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CN 4120: DESIGN II Project

PRODUCTION OF HYDROGEN VIA SYNGAS ROUTE

Overall Team Design Report

TEAM 32:

Lim Yueh Yang U046787U (Steam Methane Reformer)


Ng Su Peng U046929L (Furnace)
Ong Song Kun U046829M (High Temp. Shift Reactor)
Tham Zhi Yong, Andrew U046754W (Low Temp. Shift Reactor)
Zhang Zihong (Leader) U046816H (Pressure Swing Adsorption)
Sin Yew Leong U046835M (Heat Exchanger Network)
Heng Chee Hua U046793U (Cooling Tower)

This report is submitted in partial fulfillment of the requirements for the


Degree of Bachelor of Engineering (Chemical)

Department of Chemical & Biomolecular Engineering


National University of Singapore
2007/2008
CN 4120: Design II
Team 32 Executive Summary

EXECUTIVE SUMMARY

Hydrogen is vital for daily operations in refineries worldwide due to its primary usage
in hydrotreaters, as environmental regulations on sulphur emissions are strictly enforced.
Furthermore, secondary units, such as hydrocrackers are constructed to boost the margins of
refineries through upgrading of middle distillates (kerosene and diesel), which requires the
hydrogen. Thus this report aims to develop a preliminary design for a hydrogen plant (1.25e9
m3 (STP/year)), whose operation is based on the syngas route that involves the coupling of
steam-methane-reforming with low temperature and high temperature shift reactions. Further
assumptions such as siting the plant in Singapore and an 8000 h/year operation time were
also considered in the production of hydrogen with at least 99.9% in product purity.

The preliminary design consists of seven main units – furnace, steam-methane-


reformer (SMR), high-temperature-shift-reactor (HTS), low-temperature-shift-reactor (LTS),
pressure swing adsorber (PSA), heat exchanger network (HEN) and cooling tower.
The main purpose of the furnace was to supply heat to the feed mixture of steam and natural
gas so that the endothermic reaction can proceed in the SMR. Optimal design indicated the
requirement of a four-chamber single-tube-pass side-fired heater which comprised of a
radiant section (33m x 27m x 13m), a convection section (7m x 7m x 1m) and a stack
(diameter = 4m, height = 8m). A thermal efficiency of 94% was achieved. The refractory
walls comprised of firebricks with silicon carbide linings.

450 SMR tubes (material = HK-40) were housed in the radiant section of the furnace
where 6.0e8 kJ/h was supplied via the combustion of the tail-gas directed from PSA and
excess air. A steam-to-carbon ratio of 3:1 was stipulated, which would also minimize coking.
Prior to entering SMR, the feed was preheated to an inlet temperature of 539oC. In the
presence of Ni/Mg-Al2O4, methane would react with steam to produce an effluent that
contained primarily carbon monoxide and hydrogen. A methane conversion of 80.1% was
attained with an exit temperature of 852oC. The total cost of the SMR tubes and furnace were
estimated to be US$730,000 and US$37 million respectively.
The SMR effluent was subsequently cooled before entering HTS at a temperature of 354oC,

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32 Executive Summary

with make-up steam to achieve a steam-to-carbon ratio of 5:1. The HTS vessel (diameter =
3.46 m, height = 12.11 m, material = ASTM A387) served to increase the hydrogen yield
through the oxidation of carbon monoxide to carbon dioxide, in the presence of chromium
promoted iron oxide. The stream composition of carbon monoxide was subsequently reduced
from 13.3% to 3%. The calculated bare module cost was approximately US$3.6 million.

As the oxidation process was slightly exothermic, a lower temperature operation


would favour a higher conversion, thus justifying further process cooling to 220oC prior to
entering LTS. Through the optimal design of the LTS vessel (diameter = 3.31 m, height =
5.07 m, material = ASTM A387) with copper-zinc oxide catalyst supported on alumina, the
carbon monoxide level was further lowered to 0.5% at the LTS exit. To prevent poisoning of
PSA catalyst downstream by condensate, a knock-out drum and a bed of silica gel was
installed after LTS, prior to the entry into PSA. The bare-module cost of LTS was estimated
at US$1.4 million.

Further cooling of the LTS effluent to 50oC was effected before entering into the
knock-out drum and subsequently into PSA. The composition of the PSA feed was roughly
75% hydrogen and 18% carbon dioxide. A Polybed system of 8 columns (diameter = 3 m,
height = 8.5 m, material = SS clad), operating between 1 and 25 bar at 50oC, was adopted for
the purification of hydrogen with the use of activated carbon and zeolite 5A at a ratio of 5:1.
A hydrogen recovery of 85% with a product purity of 99.9% was subsequently achieved. The
estimated bare module cost of PSA was $25 million.

Extensive heat integration was performed for maximum energy recovery in this
design. Only cold utilities, such as high pressure steam and cooling water were needed, as the
furnace had fulfilled all the heating requirements of the plant. This resulted in the presence of
a utility pinch, which requires the adoption of pinch analysis. 3 networks each satisfying the
maximum energy recovery criterion was designed using HX-Net. The selected network was
chosen based on the lowest total annual cost and operational considerations, attaining
100.6 % of the total cost target. The chosen TEMA configuration of the heat exchangers was
that of AES shell and tube exchangers (split-ring floating head). For thermal design, the heat

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32 Executive Summary

exchanger chosen possessed a heat transfer area of 519.2 m2 (calculated by HX-Net) with 456
SS tubes of length 4.88 m while the shell was fabricated from carbon steel. The cost of this
heat exchanger was about US$526,000.

A cooling tower was designed based on an induced draft counter-flow configuration.


A filled height of 6.0 m was essential for the rejection of heat into the atmosphere via both
evaporation and sensible means. Replenishment of water (188 m3/h) was required for
continuous operation due to evaporative losses. Construction costs were estimated at
US$941,000. The lifespan of all catalysts was assumed to be 3 years and their cost amounted
to roughly US$2.2 million/year. Based on a discounted cash flow rate of return of 10% and a
payback period of 15 years (inclusive of 2 years of construction), the selling price of
hydrogen calculated was US$2.43 / kg (STP), which was less than US$2.70 / kg (STP)1.
Therefore, we recommend the construction of the plant due to the profitability of the product.

Safety is paramount, thus a HAZOP worksheet was generated to identify potential


hazards due to possible deviations in both SMR and furnace operations. Recommended
safeguards and actions were also highlighted. A summary of occupational safety and health,
environmental impact assessment and plant layout was further discussed in this report. Lastly,
an implementation of process controls and instrumentations was performed on both SMR and
furnace. A piping and instrumentation diagram (P&ID) was subsequently developed with
further discussions centering on the various reflected control strategies.

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32 Executive Summary

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32 Executive Summary

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32 Executive Summary

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32 Executive Summary

REFERENCE

1. Hydrogen and Clean Fuels: Systems Studies. Retrieved on April 17, 2008 from National
Energy Technology Laboratory Web site:
http://www.netl.doe.gov/technologies/hydrogen_clean_fuels/systems_studies.html

ACKNOWLEDGEMENTS

This section dedicates acknowledgements to all who have helped our team by offering
their valuable advice. In particular, we would like to express our heart-felt gratitude to our
professors, Prof Karimi, Prof Rangaiah, Prof Farooq, A/P Kawi, A/P M.P. Srinivasan, A/P R.
Srinivasan, A/P Krishnaswamy, A/P Hidajat and A/P Borgna, for their valuable insights.

Last but not least, this work would not have been possible without the coordination
and teamwork in Team 32 (CN4120 – Sem 2 of AY2007/08), hence we would like to thank
all of them for their assistance and understanding.

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32 Process Flow Diagram (P.F.D.)

SMR
HTS

Furnace
LTS & K/O Drum

PSA

Production of Hydrogen via Syngas Route


CN 4120: Design II
Team 32

TABLE OF CONTENTS
Chapter 1 : PROBLEM DESCRIPTION........................................................................ 1-1
1.1 PROBLEM STATEMENT FOR PLANT DESIGN SPECIFICATIONS ............ 1-1
1.2 BACKGROUND FOR DEVELOPMENT IN HYDROGEN PRODUCTION .... 1-1
1.2.1 Energy Woes – Away from Fossil Fuels Era ................................................... 1-1
1.2.2 Identifying & Justifying the Production Route – SMR .................................. 1-2
1.2.3 Choice and Significance of Reforming Feedstock – Natural Gas................... 1-4
1.2.4 Steam Methane Reforming (SMR) Reactor .................................................... 1-5
1.2.5 Furnace ............................................................................................................ 1-6
1.2.6 Shift Reactions ................................................................................................. 1-7
1.2.7 Product Purifications ....................................................................................... 1-7
1.2.8 Heat Integration ............................................................................................... 1-8
1.2.9 Cooling Requirements ..................................................................................... 1-9
1.2.10 Use of HYSYS Simulation ........................................................................... 1-10
1.3 REFERENCES ..................................................................................................... 1-10
Chapter 2 STEAM METHANE REFORMER ............................................................... 2-1
2.1 PROBLEM STATEMENT .................................................................................... 2-1
2.1.1 Problem and Specifications ............................................................................. 2-1
2.1.2 Justifications for using SMR ........................................................................... 2-1
2.2 DESIGN METHODOLOGY & PROCESS DESIGN........................................... 2-2
2.2.1 Outline of Design Methodology ....................................................................... 2-2
2.2.2 Reaction Chemistries ....................................................................................... 2-2
2.2.2.1 Effects of Temperature and Pressure – Revisiting Le Chatelier’s
Principle ............................................................................................................ 2-3
2.2.2.2 Coke Formation, Steam:Methane ratio & Inclusion of CO2 in feed ... 2-3
2.2.3 Choice of Reactor – Tubular Reformer .......................................................... 2-4
2.2.4 Justifications for Choice of Firing Configuration – Side-fired reformer
furnace ...................................................................................................................... 2-5
2.2.5 Justifications for Choice of Fluid Package – Peng-Robinson ......................... 2-6
2.2.6 Choice of Catalyst ............................................................................................ 2-6
2.2.7 Kinetics, Ni-based Catalyst & Role of Support .............................................. 2-7
2.2.8 Justification for Choice of Reactor Inlet Conditions ...................................... 2-7
2.3 PRELIMINARY DESIGN ..................................................................................... 2-8
2.3.1 Establishment of Base Case ............................................................................. 2-8

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Team 32

2.3.2 Preliminary Simulation using HYSYS ............................................................ 2-8


2.4 DETAILED DESIGN ........................................................................................... 2-10
2.4.1 Development of Critical Profiles via MATLAB & Optimisation ................. 2-10
2.4.2 Design Equations & Key Assumptions.......................................................... 2-10
2.4.3 Fitting into HYSYS Simulation Environment using Plug-Flow Reactor (PFR)
................................................................................................................................. 2-12
2.4.4 Results and Discussions ................................................................................. 2-12
2.4.4.1 Conversion profiles for CH4 and CO2 ............................................... 2-12
2.4.4.2 Temperature and Pressure Variations ............................................... 2-13
2.4.4.3 Component Mole Fractions ................................................................. 2-14
2.4.5 Optimization .................................................................................................. 2-15
2.4.6 Operating Conditions & Streams Conditions ............................................... 2-17
2.5 MATERIALS OF CONSTRUCTION & SIZING .............................................. 2-18
2.5.1 Selection Methodology ................................................................................... 2-18
2.5.2 Justifications for selecting from different grades of stainless steels ............. 2-18
2.5.3 Tube life estimation, Minimum Stress Rupture & Identification of Choice
Material................................................................................................................... 2-19
2.5.4 Sizing – Computation for Tube Thickness .................................................... 2-21
2.5.5 Sizing – Summary .......................................................................................... 2-21
2.6 ECONOMICS & SAFETY CONSIDERATIONS .............................................. 2-22
2.6.1 Economic Analysis (Brief) ............................................................................. 2-22
2.6.2 Safety Consideration for Reactor Design ...................................................... 2-22
2.7 LEARNING & CONCLUSIONS ......................................................................... 2-23
2.8 NOTATIONS ........................................................................................................ 2-24
2.9 FIGURES AND TABLES .................................................................................... 2-25
2.10 ACKNOWLEDGEMENTS................................................................................ 2-25
2.11 REFERENCES ................................................................................................... 2-26
2.12 APPENDIX ......................................................................................................... 2-28
2.12.1 MATLAB Code ............................................................................................ 2-28
2.12.1.1 Main m-file to resolve O.D.E.s .......................................................... 2-28
2.12.1.2 Function m-file to define reactions conditions and O.D.E.s ............. 2-29
2.12.2 List of Equations .......................................................................................... 2-33
2.12.2.1 Rate Equations for reactions and species for 4 O.D.E.s ................... 2-33
2.12.2.2 Mole Fractions for species ................................................................. 2-33

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Team 32

2.12.2.3 Effectiveness Factors for reactions and species ................................ 2-33


2.12.2.4 Rate & Adsorption constants for reactions 1, 2 and 3 ................................. 2-34
2.12.2.5 Adsorption constants for species .................................................................. 2-34
2.12.2.6 Heat Capacities ............................................................................................. 2-35
2.12.3 Sample Calculations..................................................................................... 2-35
2.12.4 Typical Natural Gas Compositions ............................................................. 2-35
Chapter 3 : FURNACE .................................................................................................... 3-1
3.1 INTRODUCTION .................................................................................................. 3-1
3.1.1 Furnace design methodology ........................................................................... 3-1
3.1.2 Heat transfer process in fired heater .............................................................. 3-2
3.2 RADIATION ZONE DESIGN ............................................................................... 3-2
3.2.1 Thermal Efficiency of Fired Heater ................................................................ 3-2
3.2.2 Calculation for the number of reformer tubes ............................................... 3-6
3.2.3 Calculation for mass velocity in reformer tubes ............................................. 3-7
3.2.4 Calculation of reformer tube thickness ........................................................... 3-8
3.2.5 Selection of material for reactor tube in radiation section ............................. 3-9
3.2.6 Reformer inner tube diameter....................................................................... 3-11
3.2.7 Furnace layout and design ............................................................................. 3-11
3.2.7.1 Side Fired Heater................................................................................. 3-11
3.2.7.2 Distance between burners ................................................................... 3-12
3.2.7.3 Burners used at Side Walls ................................................................. 3-13
3.2.7.4 Determination of number of burners.................................................. 3-14
3.2.8 Computations for flue gas temperature ........................................................ 3-15
3.2.8.1 Cold plane area .................................................................................... 3-15
3.2.8.2 Refractory area .................................................................................... 3-15
3.2.8.3 Absorptivity, α ..................................................................................... 3-15
3.2.8.4 Sum of product of area and the absorptivities in the radiant zone.... 3-15
3.2.8.5 Mean beam length ............................................................................... 3-16
3.2.8.6 Partial pressure of CO2 and H2O ....................................................... 3-16
3.2.8.7 Product of partial pressure and mean beam length ........................... 3-16
3.2.8.8 Mean refractory tube wall temperature ............................................. 3-16
3.2.8.9 Two main equations that will be used for iteration to find Tg (flue gas
temp) ................................................................................................................ 3-16
3.2.8.9.1 Radiant zone heat transfer ........................................................... 3-16

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Team 32

3.2.8.9.2 Radiant zone heat balance ............................................................ 3-16


3.2.8.9.3 Enthalpy of the flue gas as a function of Tg (flue gas temp)........ 3-17
3.2.8.9.4 Emissitivity of the gas Ф ............................................................... 3-17
3.2.8.9.5 Exchange factor F ......................................................................... 3-17
3.2.9 Residence Time .............................................................................................. 3-18
3.3 CONVECTION SECTION .................................................................................. 3-19
3.3.1 Convection design – Finned tubes ................................................................. 3-19
3.3.2 Design parameters for convection tubes ....................................................... 3-21
3.3.3 Pressure drop in the tubes present in furnace .............................................. 3-22
3.4 STACK DESIGN .................................................................................................. 3-24
3.4.1 Stack diameter ............................................................................................... 3-24
3.4.2 Pressure Drop across stack............................................................................ 3-24
3.4.2.1 Stack exit loss ....................................................................................... 3-24
3.4.2.2 Frictional Loss in stacks and ducts ..................................................... 3-24
3.4.2.3 Stack entrance loss .............................................................................. 3-25
3.4.2.4 Flue gas pressure drop through the convection section ..................... 3-25
3.4.2.5 Pressure drop at the top of the radiant section .................................. 3-25
3.4.2.6 Pressure gain at the convection section............................................... 3-25
3.4.3 Stack Height ................................................................................................... 3-26
3.5 MATERIALS FOR CONSTRUCTION OF FURNACE BODY & ADDITIONAL
AUXILIARIES ........................................................................................................... 3-27
3.5.1 Refractory walls ............................................................................................. 3-27
3.5.2 Stack Walls..................................................................................................... 3-28
3.5.3 Additional auxiliaries..................................................................................... 3-28
3.5.3.1 Air Preheaters ...................................................................................... 3-28
3.5.3.2 Forced Draft Fan ................................................................................. 3-29
3.5.3.3 Induced Draft Fan ............................................................................... 3-29
3.6 COST ANALYSIS ................................................................................................ 3-30
3.6.1 Purchased Equipment Costs.......................................................................... 3-30
3.6.1.1 Costing for Furnace ............................................................................. 3-30
3.6.1.2 Costing for Air Preheater .................................................................... 3-31
3.6.1.3 Costing for Induced Draft Fan and Forced Draft Fan for Air
Preheating System ........................................................................................... 3-31
3.6.1.4 Burners ................................................................................................ 3-32

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Team 32

3.6.2 Utility Cost ..................................................................................................... 3-32


3.6.2.1 Electricity cost ..................................................................................... 3-32
3.6.3 Total Annual cost ........................................................................................... 3-32
3.7 SUMMARY & CONCLUSION ........................................................................... 3-33
3.8 SPECIFICATION OF FIRED-HEATER ........................................................... 3-34
3.9 REFERENCES ..................................................................................................... 3-35
Chapter 4 : HIGH TEMPERATURE SHIFT REACTOR............................................. 4-1
4.1 INTRODUCTION .................................................................................................. 4-1
4.1.1 Water gas shift ................................................................................................. 4-1
4.1.2 High temperature shift .................................................................................... 4-2
4.2 PROBLEM DESCRIPTION.................................................................................. 4-3
4.3 REACTION THERMODYNAMICS .................................................................... 4-6
4.3.1 Criteria for Chemical Reaction Equilibrium .................................................. 4-6
4.3.2 Effects of Pressure on Reaction Equilibrium.................................................. 4-7
4.3.3 Effects of Temperature on Reaction Equilibrium .......................................... 4-8
4.4 REACTION KINETICS ...................................................................................... 4-11
4.5 CATALYST .......................................................................................................... 4-12
4.6 REACTOR............................................................................................................ 4-13
4.6.1 Type of reactor ............................................................................................... 4-13
4.6.2 Reactor design ................................................................................................ 4-13
4.7 METHODOLOGY AND CALCULATIONS ...................................................... 4-16
4.7.1 Weight of catalyst .......................................................................................... 4-16
4.7.2 Pressure drop ................................................................................................. 4-19
4.7.3 Thickness of vessel ......................................................................................... 4-24
4.7.4 Reactor size and cost ...................................................................................... 4-24
4.8 HEAT EXCHANGER .......................................................................................... 4-26
4.8.1 Heat Exchanger Design Considerations ........................................................ 4-27
4.8.1.1 Physical properties extraction ........................................................................ 4-27
4.8.1.2 Determination of overall heat transfer coefficient......................................... 4-28
4.8.1.3 Exchanger type and dimensions ..................................................................... 4-28
4.8.1.4 Heat transfer area........................................................................................... 4-29
4.8.1.5 Layout and tube size ....................................................................................... 4-29
4.8.1.6 Number of tubes ............................................................................................. 4-29
4.8.1.7 Bundle and shell diameter .............................................................................. 4-29

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CN 4120: Design II
Team 32

4.8.1.8 Tube-side heat transfer coefficient ................................................................. 4-30


4.8.1.9 Shell-side heat transfer coefficient ................................................................. 4-30
4.8.1.10 Overall coefficient ......................................................................................... 4-31
4.8.1.11 Pressure drop ................................................................................................ 4-31
4.9 CONCLUSION ..................................................................................................... 4-32
4.10 NOTATIONS ...................................................................................................... 4-33
4.11 REFERENCES ................................................................................................... 4-35
4.12 APPENDICES .................................................................................................... 4-36
Appendix 4.12.1 .......................................................................................................... 4-36
Appendix 4.12.2 .......................................................................................................... 4-38
Appendix 4.12.3 .......................................................................................................... 4-39
Chapter 5 : LOW TEMPERATURE SHIFT REACTOR .............................................. 5-1
5.1 INTRODUCTION .................................................................................................. 5-1
5.2 LTS DESIGN CONSIDERATIONS ...................................................................... 5-2
5.2.1 Current Status ................................................................................................. 5-2
5.2.2 Kinetics of Low-Temperature Water-Gas-Shift (LTWGS) ........................ 5-3
5.2.2.1 Assumption made for equation (5-3) : .................................................. 5-4
5.2.3 LTS Catalyst .................................................................................................... 5-5
5.2.3.1 Characteristics of the industrial LTS catalyst ...................................... 5-6
5.2.3.2 Preparation ............................................................................................ 5-6
5.2.3.3 Supply .................................................................................................... 5-6
5.2.3.4 Deactivation of LTS Catalyst ................................................................ 5-7
5.2.3.5 LTS catalyst in operation ...................................................................... 5-8
5.2.3.6 Assumptions made for LTS Catalyst .................................................... 5-9
5.2.3.7 Mass balance on the Copper-Zinc catalyst pellet ................................. 5-9
5.2.3.8 Heat balance on the Copper-Zinc catalyst pellet................................ 5-10
5.2.4 Modeling the converter ............................................................................. 5-12
5.2.4.1 Assumptions made for the converter ................................................ 5-12
5.2.4.2 Reactor mass balance .......................................................................... 5-12
5.2.4.3 Reactor mass balance .......................................................................... 5-13
5.3 DESIGN CONDITIONS ...................................................................................... 5-17
5.3.1 Temperature .................................................................................................. 5-17
5.3.2 Pressure .......................................................................................................... 5-17
5.3.3 Steam to CO ratio .......................................................................................... 5-17

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CN 4120: Design II
Team 32

5.3.4 Design Procedure for LTS outlet compositions and Mass of Catalyst used 5-19
5.3.5 LTS outlet compositions and Mass of Catalysts used ................................... 5-20
5.3.6 Design Procedure for Aspect Ratio ............................................................... 5-21
5.3.7 Results for Aspect Ratio ................................................................................ 5-22
5.3.8 Design Procedure for the dimensions of bed and thickness of vessel wall ... 5-23
5.3.9 Results for bed dimensions and wall thickness ............................................. 5-24
5.3.10 Allowances set for design ............................................................................. 5-25
5.3.11 Study of controlling parameters ................................................................ 5-26
5.4 CHOICE OF A REACTOR BED ........................................................................ 5-27
5.4.1 Cost estimation for the LTS converter .......................................................... 5-28
5.5 DESIGN OF THE KNOCK-OUT DRUM........................................................... 5-30
5.5.1 Working principle of the knock-out drum .................................................. 5-30
5.5.2 Sizing of the knock-out drum ........................................................................ 5-30
5.5.3 Results and cost estimation............................................................................ 5-31
LITERATURE REVIEW .......................................................................................... 5-33
CONCLUSION .......................................................................................................... 5-35
BIBLIOGRAPHY ...................................................................................................... 5-36
APPENDIX A1 ........................................................................................................... 5-37
APPENDIX A2 ........................................................................................................... 5-39
APPENDIX A3 ........................................................................................................... 5-39
Chapter 6 : PRESSURE SWING ABSORPTION .......................................................... 6-1
6.1 INTRODUCTION .................................................................................................. 6-1
6.2 PROBLEM STATEMENT .................................................................................... 6-2
6.3 THEORETICAL BACKGROUND ....................................................................... 6-2
6.3.1 Separation via adsorption................................................................................ 6-2
6.3.2 Pressure-Swing Adsorption (PSA) .................................................................. 6-3
6.3.3 Skarstrom Cycle............................................................................................... 6-3
6.3.4 Adsorbents ....................................................................................................... 6-4
6.4 DESIGN CONSIDERATIONS .............................................................................. 6-5
6.5 ACTUAL MODELING OF PSA ........................................................................... 6-7
6.5.1 Component Mass Balance ............................................................................... 6-8
6.5.2 Overall Mass Balance ...................................................................................... 6-8
6.5.3 Pressure terms.................................................................................................. 6-8
6.5.4 Adsorption rates .............................................................................................. 6-8

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CN 4120: Design II
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6.5.5 Overall Mass Balance in Dimensionless Form ................................................ 6-9


6.5.6 Component Mass Balance in Dimensionless Form ......................................... 6-9
6.5.7 Dimensionless Pressure terms ......................................................................... 6-9
6.5.8 Dimensionless Langmuir Adsorption Isotherms ............................................ 6-9
6.5.9 Boundary Conditions ..................................................................................... 6-10
6.6 MODEL OPTIMIZATION.................................................................................. 6-11
6.6.1. Process Methodology .................................................................................... 6-12
6.6.2 Initial approximation of the adsorption time from the breakthrough curve... 6-
13
6.6.3 Determination of Cyclic steady state ............................................................. 6-14
6.6.4 Refinement of the pressurization time .......................................................... 6-15
6.6.5 Possible optimization of feed superficial velocity and diameter of the bed . 6-16
6.7 FINAL RESULTS AND DISCUSSIONS ............................................................ 6-18
6.8 COST ESTIMATIONS ........................................................................................ 6-19
6.9 CONCLUSION ..................................................................................................... 6-22
6.10 NOTATIONS ...................................................................................................... 6-23
6.11 APPENDIX ......................................................................................................... 6-25
6.12 CONSTANTS APPLIED IN COMSOL SIMULATION .................................. 6-29
6.13 REFERENCES ................................................................................................... 6-30
Chapter 7 : HEAT EXCHANGER NETWORK ............................................................ 7-1
EXECUTIVE SUMMARY .......................................................................................... 7-1
ACKNOWLEDGEMENTS ......................................................................................... 7-1
7.1 DESIGN METHODOLOGY OF A HEAT EXCHANGER NETWORK ............ 7-2
7.1.1 Determination & Verification of Stream Data Properties Extracted from
Hysys ......................................................................................................................... 7-2
7.1.1.1 Calculations of Maximum Design Velocities ........................................ 7-2
7.1.1.2 Determination of Flow Area Diameter ................................................. 7-3
7.1.1.3 Calculations of Convective Heat Transfer Coefficients (HTC) ........... 7-4
7.1.1.4 Fouling Factors ...................................................................................... 7-5
7.2 TARGETING ......................................................................................................... 7-6
7.2.1 Cost Considerations ......................................................................................... 7-6
7.2.2 Utility Cost Calculations .................................................................................. 7-8
7.2.3 Heat Exchanger Capital Cost Estimations...................................................... 7-9
7.2.4 Supertargeting ................................................................................................. 7-9

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7.2.5 Comparison between the usage of HP and LP Steam Generation ............... 7-10
7.2.6 Calculation of Utility Targets ........................................................................ 7-10
7.3 MER NETWORK DESIGN................................................................................. 7-12
7.3.1 Stream matching above pinch ....................................................................... 7-14
7.3.2 Stream matching below pinch ....................................................................... 7-14
7.3.3 Number of units in MER network................................................................. 7-15
7.3.4 Alternative MER Network Designs for Consideration ................................. 7-15
7.3.4.1 Network 1a ........................................................................................... 7-15
7.3.4.2 Network 1b........................................................................................... 7-16
7.4 NETWORK EVOLUTION .................................................................................. 7-20
7.4.1 Steps involved in network evolution.............................................................. 7-20
7.4.2 Evolution of 1st loop ....................................................................................... 7-20
7.4.3 Evolution of 2nd loop ...................................................................................... 7-21
7.5 HEAT EXCHANGER DESIGN .......................................................................... 7-26
7.5.1 Stream Data ................................................................................................... 7-26
7.5.2 Material of Construction ............................................................................... 7-27
7.5.3 Shell and Tube-Side Fluid Allocation ........................................................... 7-27
7.5.4 Exchanger Type ............................................................................................. 7-28
7.5.5 Baffles ............................................................................................................. 7-28
7.5.6 Tube Dimensions ............................................................................................ 7-28
7.5.7 Tube Arrangements ....................................................................................... 7-29
7.5.8 Calculations .................................................................................................... 7-29
7.5.8.1 Tube-Side Heat Transfer Coefficient Calculations ............................ 7-31
7.5.8.2 Shell-Side Heat Transfer Coefficient Calculations ............................. 7-31
7.5.8.3 Overall Heat Transfer Coefficient Calculations ................................. 7-33
7.5.8.4 Tube-Side Pressure Drop Calculations ............................................... 7-33
7.5.8.5 Shell-Side Pressure Drop Calculations ............................................... 7-34
7.5.9 Modification of Design ................................................................................... 7-34
7.5.10 Exchanger Cost ............................................................................................ 7-35
7.6 RECENT DEVELOPMENTS ................................................................................. 7-36
7.7 HEAT EXCHANGER SPECIFICATION SHEET............................................. 7-37
7.8 INTEGRATED HEN WITH PFD OF PROPOSED HYDROGEN PLANT ..... 7-38
APPENDIX A – STREAM DATA ............................................................................. 7-39
REFERENCE ............................................................................................................. 7-40

Production of Hydrogen via Syngas Route ix


CN 4120: Design II
Team 32

Chapter 8 : COOLING TOWER .................................................................................... 8-1


8.1 PROBLEM STATEMENT .................................................................................... 8-1
8.2 WORKING PRINCIPLES OF COOLING TOWER ........................................... 8-2
8.3 Preliminary Design ................................................................................................. 8-3
8.3.1 Selection of cooling tower ................................................................................ 8-3
8.3.1.1 Justification to reject the use of natural draft tower ............................ 8-3
8.3.1.2 Justification to use induced draft tower ............................................... 8-4
8.3.2 Comparison between counter-flow and cross-flow Pattern ........................... 8-4
8.4 DETAILED DESIGN OF COOLING TOWER ................................................... 8-5
8.4.1 Specification of cooling tower design parameters........................................... 8-5
8.4.1.1 Wet bulb temperature ........................................................................... 8-5
8.4.1.2 Range ..................................................................................................... 8-5
8.4.1.3 Cooling water requirement ................................................................... 8-6
8.4.1.4 Approach ............................................................................................... 8-6
8.4.2 Exit air temperature and water to air flow ratio (L/G) .................................. 8-6
8.4.2.1 Exit air temperature .............................................................................. 8-6
8.4.2.2 Water to air flow (L/G) ratio................................................................. 8-7
8.4.3 Cooling tower characteristic............................................................................ 8-7
8.4.4 Loading factor .................................................................................................. 8-8
8.4.5 Dimensions of Tower ......................................................................................... 8-10
8.4.5.1 Fill Height ............................................................................................ 8-10
8.4.5.2 Base area .............................................................................................. 8-10
8.4.5.3 Fill volume ........................................................................................... 8-10
8.4.6 Make-up Water Requirement ....................................................................... 8-11
8.4.6.1 Evaporation loss (E) ............................................................................ 8-11
8.4.6.2 Drift loss (D)......................................................................................... 8-11
8.4.6.3 Blow-down (B) ..................................................................................... 8-11
8.4.6.4 Makeup water requirement (M) ......................................................... 8-12
8.4.7 Power Requirement ....................................................................................... 8-12
8.4.7.1 Pump power (Pp).................................................................................. 8-12
8.4.7.2 Fan Power (PF)..................................................................................... 8-13
8.5 COOLING TOWER INTERNALS ..................................................................... 8-14
8.5.1 Liquid Distributor.......................................................................................... 8-14
8.5.2 Fill................................................................................................................... 8-15

Production of Hydrogen via Syngas Route x


CN 4120: Design II
Team 32

8.5.3 Drift Eliminators ............................................................................................ 8-15


8.5.4 Supports ......................................................................................................... 8-16
8.5.5 Cooling tower basin ....................................................................................... 8-16
8.6 MATERIAL OF CONSTRUCTION ................................................................... 8-17
8.6.1 Liquid Distributor.......................................................................................... 8-17
8.6.2 Fills ................................................................................................................. 8-18
8.6.3 Drift eliminator .............................................................................................. 8-18
8.6.4 Mechanical support ....................................................................................... 8-18
8.7 COST ANALYSIS ................................................................................................ 8-19
8.7.1 Construction cost of for cooling tower .......................................................... 8-19
8.7.2 Operating Cost ............................................................................................... 8-20
8.7.2.1 Cost of makeup water .......................................................................... 8-20
8.7.2.2 Cost of Electricity ................................................................................ 8-20
8.7.2 Optimization between the operating and construction cost ......................... 8-21
8.8 ADDITIONAL CONSIDERATIONS TO COOLING TOWER DESIGN ........ 8-22
8.8.1 Water Treatment ........................................................................................... 8-22
8.8.1.1 Corrosion control................................................................................. 8-22
8.8.1.2 Scale control......................................................................................... 8-23
8.8.1.3 Biological control ................................................................................. 8-23
8.8.2 Environmental Concerns ............................................................................... 8-24
8.9 CONCLUSION ..................................................................................................... 8-25
REFERENCES........................................................................................................... 8-27
APPENDIX A IMPURITIES FOUND IN COOLING WATER .............................. 8-28
Chapter 9 : ECONOMICS & PROFITABILITY........................................................... 9-1
9.1 INTRODUCTION .................................................................................................. 9-1
9.2 ASSUMPTIONS ..................................................................................................... 9-1
9.3 CAPITAL COSTS .................................................................................................. 9-2
9.3.1 Computations for Fixed Capital ......................................................................... 9-2
9.3.2 Computations for Total Module Costs ............................................................ 9-7
9.3.3 Computations for Grassroots Costs (FCI) ...................................................... 9-7
9.3.4 Computations for Working Capital ................................................................ 9-8
9.4 MANUFACTURING COSTS ................................................................................ 9-8
9.4.1 Operating labour costs, COL .......................................................................... 9-10
9.4.2 Utility costs, CUT............................................................................................. 9-11

Production of Hydrogen via Syngas Route xi


CN 4120: Design II
Team 32

9.4.2.1 Electricity ............................................................................................. 9-11


9.4.2.2 Cooling water cost ............................................................................... 9-12
9.4.2.3 Waste treatment costs, CWT................................................................. 9-12
9.4.3 Raw materials costs, CRM .............................................................................. 9-13
9.4.4 Land lease, CL ................................................................................................ 9-13
9.4.5 Computation of manufacturing costs ............................................................ 9-14
9.4.6 Salvage value .................................................................................................. 9-15
9.4.7 Depreciation ................................................................................................... 9-15
9.4.8 Revenues......................................................................................................... 9-15
9.5 PROFITABILITY ANALYSIS............................................................................ 9-16
9.5.1 Land Cost ....................................................................................................... 9-17
9.5.2 After Tax Cash Flow ...................................................................................... 9-17
9.5.2 Rate of Return on Investment (ROROI) ....................................................... 9-18
9.5.3 Net Present Value (NPV) ............................................................................... 9-18
9.5.4 Discounted Cash Flows in Project ................................................................. 9-18
9.6 FEASIBILITY OF STORAGE FACILITIES FOR NATURAL GAS FEED ... 9-21
9.6.1 Capital Costs .................................................................................................. 9-24
9.6.2. Operating Costs ............................................................................................ 9-25
9.6.3 Overall Costs .................................................................................................. 9-25
9.6.4 Economic Compensation ............................................................................... 9-26
9.7 RECOMMENDATIONS ..................................................................................... 9-27
9.8 CONCLUSION ..................................................................................................... 9-29
REFERENCES........................................................................................................... 9-30
Chapter 10 : SAFETY, HEALTH & ENVIRONMENT (S.H.E.) ................................ 10-1
10.1 INTRODUCTION .............................................................................................. 10-1
10.2 HAZARDS AND OPERABILITY STUDIES (HAZOP) REVIEW ................. 10-2
10.3 PLANT LAYOUT ............................................................................................ 10-23
10.3.1 Segregation ................................................................................................. 10-23
10.3.2 Transportation Considerations ................................................................. 10-24
10.3.3 Administration ........................................................................................... 10-24
10.3.4 Laboratory ................................................................................................. 10-25
10.3.5 Workshop ................................................................................................... 10-25
10.3.6 Control Room............................................................................................. 10-25
10.3.7 Transformer Substation ............................................................................ 10-26

Production of Hydrogen via Syngas Route xii


CN 4120: Design II
Team 32

10.3.8 Emergency Services ................................................................................... 10-26


10.3.9 Amenities (Medical Centre and Canteen) ................................................. 10-26
10.3.10 Process and Auxiliary Units .................................................................... 10-27
10.3.10.1 Furnace (Housing SMR)................................................................ 10-27
10.3.10.2 Reactors (HTS, LTS), PSA and Knockout Drum ......................... 10-27
10.3.10.3 Cooling Tower................................................................................ 10-28
10.3.10.4 Heat Exchangers ............................................................................ 10-29
10.3.10.5 Flares .............................................................................................. 10-29
10.3.10.6 Wastewater Treatment Plant ........................................................ 10-30
10.4 OCCUPATIONAL SAFETY ........................................................................... 10-31
10.4.1 Personal Protection Equipment (PPE) ...................................................... 10-31
10.4.2 Noise ............................................................................................................... 10-32
10.4.3 Ventilation .................................................................................................. 10-33
10.5 OCCUPATIONAL HEALTH HAZARD IDENTIFICATION ...................... 10-34
10.6 ENVIRONMENTAL IMPACT ASSESSMENT ............................................. 10-38
10.6.1 Objectives ................................................................................................... 10-38
10.6.2 Risk Assessment Matrix............................................................................. 10-38
10.6.3 Elements of Environmental Impact Assessment ....................................... 10-46
10.6.3.1 Gaseous emissions ............................................................................ 10-46
10.6.3.2 Effluent discharge ............................................................................ 10-46
10.6.3.3 Waste management & minimization ............................................... 10-47
10.6.3.4 Energy efficiency ............................................................................. 10-47
10.6.4 Hydrogen Product Life Cycle Assessment ................................................ 10-48
10.6.4.1 Ramifications of Hydrogen LCA .................................................... 10-49
10.7 CONCLUSION ................................................................................................. 10-50
REFERENCES......................................................................................................... 10-51
Chapter 11 : INSTRUMETNATION & CONTROL.................................................... 11-1
11.1 INTRODUCTION .............................................................................................. 11-1
11.2 PROCESS CONSIDERATION AND DESCRIPTION .................................... 11-2
11.3 PROCESS CONTROL METHODOLOGY ...................................................... 11-3
11.4 SELECTION OF CONTROLLED, MANIPULATED AND MEASURED
VARIABLE ................................................................................................................ 11-4
11.5 DETAILED CONTROL DESIGN FOR REFORMER FEED ......................... 11-5
11.5.1 Steam-to-Methane Ratio Control ................................................................ 11-5

Production of Hydrogen via Syngas Route xiii


CN 4120: Design II
Team 32

11.5.2 Pressure Control Loop for Expander.......................................................... 11-7


11.5.3 Temperature Control Loop to Preheat SMR Feed ..................................... 11-7
11.5.4 Composition Analyzer for SMR Effluent.................................................... 11-8
11.6 DETAILED CONTROL DESIGN FOR SMR FURNACE .............................. 11-9
11.6.1 Air-to-Fuel Ratio Control ............................................................................ 11-9
11.6.2 Temperature Control Loop to Regulate Effluent Exit Temperature....... 11-10
11.6.3 Pressure Control Loop to Regulate Furnace Draft .................................. 11-11
11.6.4 Flue Gas Exit Temperature Control ......................................................... 11-12
11.6.6 Analyzers for Furnace Control.................................................................. 11-14
11.7 Safety Devices ................................................................................................... 11-14
11.7.1 Pressure Relief Valves................................................................................ 11-14
11.7.2 Process Alarms ........................................................................................... 11-15
11.7.3 Safety Interlocks or Emergency Shutdown System (SIS or ESD)............ 11-16
11.7.3.1 Implementation of SIS or ESD for the protection of nickel catalyst . 11-
17
11.8 Additional Considerations in Process Control ................................................ 11-18
11.8.1 Redundancy of Air Blowers and Expanders ............................................. 11-18
11.8.2 Isolation Valves and Bypass ...................................................................... 11-19
11.9 REFERENCES ................................................................................................. 11-19

Production of Hydrogen via Syngas Route xiv


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

Chapter 1 : PROBLEM DESCRIPTION

1.1 PROBLEM STATEMENT FOR PLANT DESIGN SPECIFICATIONS

This project requires the production of hydrogen in Singapore. This has to be


accomplished via a syngas route, which involves the governing Steam Methane Reforming
(SMR) reactions, as well as the low and high temperature shift reactions. The following
design specifications have been given and the following plant design endeavours to meet
these criteria:

 Location of Plant: Singapore


 Operation Time: 8000 hours / year
 Plant Capacity (PC): 1.25 × 109 m3(STP) / year
 Feed Composition (FC) to SMR reactor: 3 : 1 (H2O : CH4)
 % CO in H2 Specification at the exit of the shift converter: 0.7%
 Purity of hydrogen product: > 99.9% (mole)
 Natural Gas Feed: C1 = 97.7%; C2+ = 1.2%; CO2 = 0.7%; N2 = 0.4%

1.2 BACKGROUND FOR DEVELOPMENT IN HYDROGEN PRODUCTION

1.2.1 Energy Woes – Away from Fossil Fuels Era

Recent years saw the rapid developments on alternative energies, in place of their
conventional fossil fuels counterpart. The latter has several disadvantages [R4] associated with
it, including:

(i) Air pollution (formation of NOx, CO & Unburned hydrocarbons contributing to


urban ozone);
(ii) Environmental pollutions (e.g. oil spill during transport)
(iii) Global warming (emission of greenhouse gases) during combustion
(iv) Dependence of fuel supply on oil-producing nations, which could result in
dominance in oil prices

Production of Hydrogen via Syngas Route 1-1


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

Given these drawbacks, the search for an alternative fuel becomes more pertinent [R4].
One of the possible solutions is the production of hydrogen. In contrast, the latter promises:

(i) Exclusion pollution due to fossil fuels (by-product is H2O & hazards associated
with spills are minimal)
(ii) Exclusion of greenhouse gases
(iii) Removal of price dominance, from the oil-producing nations
(iv) Well-distributed production due to the ease of manufacture.

1.2.2 Identifying & Justifying the Production Route – SMR

The uses of hydrogen extend way beyond the supply for fuels. For instance, hydrogen
could be used in the petrol-chemical industries to make plastics products or it could be used
to produce ammonia in the Haber process. In addition, it has been employed in the refineries
to remove unwanted sulfur contents in crudes via the hydro-de-sulfurization (HDS) units.
Nonetheless, hydrogen does not exist on Earth naturally. To harness of the above-mentioned
uses, a plant has to be designed to produce hydrogen efficiently and safely.

Typically, several methods (Gross, 2005) [R1] are available for hydrogen production.
In the refineries, H2 can be produced in its in-house hydrogen plant or from the CRU
(Catalytic Reformer Unit). H2 produced via the coal gasification route is not aimed at H2
production, rather, it is a by-product of coke production, such as the steel industry in Asia &
Europe [R1]. With more advanced gasification processes, it could also increase the amount of
H2 from coal by a considerable extent. Meanwhile, electrolysis of water promises H2 product
of high purity, but this is dependent on the local costs for electricity. To make it economically
more viable, electricity has to be available at a lower cost. Another instance of using
electricity is the production of Cl2 and NaOH, namely the Chloroalkali process, whereby H2
is produced as a by-product. In fact, more recently, experimental works have gone underway
to produce H2 via photo-electrolysis and biomass gasification.

In this work, one of the most commonly used industrial processes has been adopted,
which is the Steam Methane Reforming (SMR), which accounts for about 45% of world H2
production. This has been illustrated by the following diagram.

Production of Hydrogen via Syngas Route 1-2


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

Fig 1-1: Distribution of hydrogen production methods in industries

Looking from the perspective of production on an industrial scale, the use of SMR
would provide the economy-of-scale by providing more opportunities for heat
integration (i.e. within SMR unit itself). This reflects a higher degree of optimization for
the usage of utilities. Typically, this can be achieved via steam generation. The latter can be
used for (i) for sale; (ii) for recycle as feed into SMR.

Meanwhile, comparing to other methods (e.g. partial oxidation, auto-thermal


reforming) of syngas production, the SMR route offered the following [R2] competitive
advantages:

 Lowest Tprocess required (better cost-savings)


 Extensive industrial experience
 Best ratio of H2 : CO for production applications of hydrogen
 Does not require O2 (cost-savings & safety enhanced)

With such encouraging advantages, the steam reforming process remains as the
most mature and established form of technology to produce hydrogen [R3].

And indeed, several companies world-wide like Haldor-Topsøe, Howe-Baker,


Foster Wheeler, Tokyo Gas Company, McDermott Technology Inc. and IDATech are
employing SMR technology to manufacture hydrogen [R3].

Production of Hydrogen via Syngas Route 1-3


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

1.2.3 Choice and Significance of Reforming Feedstock – Natural Gas

One of the major factors contributing to the operating characteristics of the reforming
applications is the choice of processing feed for the reformer. In this work, natural gas
(containing predominantly Methane, CH4) has been designated. Upon further research [R3],
few possible reasons for using natural gas include:

 Most economic & mature reforming technology


 Lower environmental impact (few emissions, except CO2)
 Supply of natural gas more readily available
 Lower risk of coking (carbon formation)

The following table adapted from literature shows the some of the noteworthy
features for the various choices of reforming feedstock:

Table 1-1: Comparison on different steam reforming feedstock

Production of Hydrogen via Syngas Route 1-4


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

1.2.4 Steam Methane Reforming (SMR) Reactor

In this design, the SMR unit has been employed to manufacture the product of interest
– Hydrogen (H2). The earlier text has described and justified the need to use SMR and to
have Methane (CH4) as the feedstock. In order to design an efficient reactor to meet the high
CH4 conversion, it is imperative to consider the key factors that played an instrumental role in
influencing the performance of the reactor.

(I) Tube Geometry (related to tube length & diameter, average heat flux & space velocity)
• ↑ Tube Length more economical than ↑ No. of tubes
 ↑ No. of tubes complicate design at reactor’s inlet and outlet.
• Limit for Tube Length
 Threat of tube bending.
 Risk of too drastic pressure drop over the catalyst bed.
• ↑ Tube diameter to be accompanied with ↑ Tube Wall thickness
 For thinner tubes, ↓ temperature required & better heat transfer (↑cost savings).
 Also, less tubes need to be used to meet required conversion.
(II) Firing Configuration (Bottom vs Top vs Terrace vs Side)
• Side-Fired Configuration (with short flames distributed along reactor wall)
 Higher level of regulatory control over Tube Wall Temperature.
 ↑ Design and operational flexibilities.
 ↑ Average Heat Flux for higher conversion.
 Endure more severe reaction conditions.
 Lower NOx levels produced in flue gas stream.
• Construction of tubes
 Higher level of regulatory control over Tube Wall Temperature.
 Creeping strength is a strong function of the choice for tube material
(III) Catalyst (intrinsic activity, surface area, microstructure, porosity, mechanical
resistance, thermal & chemical stability, resistance to carbon deposition)
• Catalyst Structure
 Provision of support to give stable micropore system, overcoming sintering
issue when process temperature is above Tamman temperature (Ni: 863K)
 Low surface area carriers employed due to high temperatures involved.
 Crux: Maximize catalyst activity & heat transfer; Minimize Pressure Drop
Table 1-2: Key design considerations for SMR reactor unit

Production of Hydrogen via Syngas Route 1-5


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

The SMR reactor typically consists of multiple catalyst-loaded tubes housed within a
furnace. The latter provides the much-needed heat duty due to the characteristic endothermic
reforming reactions, in which CH4 reacts with steam to give the desired H2 product. Given
that the SMR unit represents the heart of the operations for the plant, it is essential for us to
fulfill the key design considerations, as given in Table 1-2.

1.2.5 Furnace

The furnace provides heat to support the endothermic SMR reactions. In this design,
the fuel feed used for the combustion is harnessed from the purge stream of the Pressure
Swing Adsorption (PSA) unit, considering its high H2 (as compared to CH4) content.
However, this purge stream has high carbon dioxide (CO2) content, which does not support
combustion. Consequently, an amine scrubber is also proposed to remove this undesired CO2.
Nonetheless, in the event of insufficient fuel supply by the PSA purge stream, it is
recommended to make up with a natural gas fuel feed. This could originate from the
feedstock of SMR reactor. It is noteworthy that combustion typically occurs at atmospheric
pressure, hence, an expander is to be installed to decrease the pressure of the SMR natural gas
feedstock, before allowing the fuel to proceed to the burner.

To demonstrate the advantages conferred by the side-fired configuration, small


premix burners would line up along the walls of the straight wall furnace, as such burners
provide short flame length and ease for temperature control. The flue gas generated from the
combustion process carries a net amount of heat for which is transported upward to the
convection section through the use of induced draft fan. The heat carried by the flue gas is
then used to heat up the process streams passing through the convection section.

In the convection section, steam is generated within the tubes closest to the radiation
section. This is followed by two other process streams, namely, SMR feed and combustible
air. Steam generation is situated closest to the radiation section because heat transfer is most
efficient for heat exchange between two different phases. Through effective process control
and instrumentation, the process variables within the furnace are kept constant. This helps to
maintain the product yield, while keeping the operating environment safe.

Production of Hydrogen via Syngas Route 1-6


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

1.2.6 Shift Reactions

The main purpose of the high temperature shift reactor is to derive more H2 from the
one of the SMR products, carbon monoxide (CO). The feed into the High Temperature Shift
(HTS) reactor is at a relatively high level of CO as it exits from the steam methane reformer.
This CO was reacted with steam to form more H2 with the following water gas shift equation:
CO + H 2 O ⇔ CO2 + H 2 ∆H rxn = −44.447 kJ / mol

There is a need to couple the high temperature shift reaction with a low temperature
shift (LTS) reaction because of the exothermic nature of the water gas shift reaction.
Therefore, high conversion occurs at low temperatures. However, the rate of reaction is too
slow (i.e. compromised) at low temperatures. Thus, the HTS reactor is employed to ensure a
high reaction rate, while its LTS counterpart maintains the required conversion.

Based on iron oxide as the catalyst, the design of the HTS was able to convert a
13.34% CO feed, to 3.0% CO, after which it is fed into the LTS. The designed conversion of
the high temperature shift reactor was 75.27%. Due to the adiabatic reaction in high
temperature shift, the temperature of the feed was raised from 627K to 692K.

The feed was cooled to 493K prior to entry into the low temperature shift reactor,
which employed the Copper-Zinc Oxide catalyst supported on alumina. A CO conversion
efficiency of 82.9% was obtained, which corresponds to a 0.5mol% CO (dry basis) in the
outlet stream of the LTS. This product stream was then transferred to the knock-out drum,
where liquid water was separated from the other gaseous products. The latter then flowed to
the PSA columns for further purification.

1.2.7 Product Purifications

For this design, pressure swing adsorption (PSA) was adopted as the preferred mode
of purification due to the stated requirement of attaining 99.9% in product purity, which
otherwise was not achievable through the conventional use of a CO2 scrubber and a
methanator (95–97%).

Production of Hydrogen via Syngas Route 1-7


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

The high concentration of hydrogen (75% at the entrance) could lead to possible
hydrogen embrittlement, thus the material of construction chosen was carbon steel clad with
stainless steel as this material possessed a lower material factor as compared to stainless steel,
which translated to a lower bare module cost (1.8 vs 3).

Through the prior installation silica gel, the amount of water entering PSA after
exiting the knockout drum was assumed to be negligible. Thus the chosen adsorbents for PSA
were activated carbon and zeolite 5A. Activated carbon was utilized to remove hydrocarbons,
such as CH4, C2+ and CO2 due to the preferential adsorption isotherms that these components
exhibit with activated carbon. Similarly, zeolite 5A was employed to remove CO and N2.
According to the Polybed design, this comprises of 7-10 beds with the incorporation of
various operation steps, such as pressurization, high pressure adsorption, blowdown and
purge, a final product of 99.9% purity and 85% hydrogen recovery was attainable.
Subsequently, the PSA tail gas was routed to the furnace as a source of fuel for combustion.

1.2.8 Heat Integration

Energy integration involves the usage of process streams within the plant itself to
fulfil the heating and cooling requirements at various points of the process. An optimal
solution would be of utmost importance in a chemical plant, as this would help to mitigate the
rising cost of utilities associated with increased fuel cost. Therefore, to achieve optimal heat
integration, the systematic development of a heat exchange network (HEN) would have to be
carried out.

The usage of a HEN would be an integral step in the maximization of energy recovery.
The use of pinch analysis would be critical in lessening the requirements for hot and cold
utilities, which are major components of the operating cost of the hydrogen plant. However,
this must be balanced with the increased capital investment associated with the installation of
heat exchangers.

It was found that a furnace was required to provide the necessary heat of reaction for
SMR in normal operation. Preliminary calculations showed that the large amount of heat
produced by the furnace provided for the entire heating requirement in the hydrogen plant.

Production of Hydrogen via Syngas Route 1-8


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

This results in the lack of need for hot utilities, i.e. a threshold problem ensued with
only cold utilities required. Hence, possible cold utilities to be considered would be the
generation of high or low pressure steam, and the usage of cooling water to cool low-grade
heat. This could result in the presence of a utility pinch, which would be tackled by a similar
application of pinch analysis, treating the utility stream as a dummy process stream. A
multitude of network variations and possible evolution of the network would also be
considered to obtain the most economical and practical solution for the energy integration of
the designed hydrogen plant.

1.2.9 Cooling Requirements

The main purpose of the cooling tower is to reject the low grade heat absorbed from
process stream into the atmosphere by means of latent heat of evaporation and sensible heat
transfer. The cooling tower in this hydrogen plant is designed to provide a continuous flow of
cooling water required for the condensation and elimination of water vapor in the outlet
stream of the LTS reactor, before it is fed into the PSA columns for purification of H2 and
removal of CO2.

The design of the cooling tower is based on an induced draft counter-flow


configuration. This is because this type of configuration does not experience any recirculation
which can cause a drop in cooling tower efficiency due to higher wet bulb temperature and in
the long run, it is more economical due to lower power requirement for auxiliary units such
as fans and pumps.

In the design of this cooling tower, it is assumed by heuristic that the maximum inlet
temperature of cooling water to be 120˚F and cooling water exit temperature to be 90˚F and
the ambient wet bulb temperature is derived from the average daily maximum dry bulb
temperature and mean humidity. Hence, the performance of the cooling tower can be
optimized by manipulating the exit air temperature and it is found to be 105˚F, which is the
average of the inlet and outlet water temperature.

Production of Hydrogen via Syngas Route 1-9


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

1.2.10 Use of HYSYS Simulation

The simulation of the hydrogen plant was performed in Hysys. Care must be
exercised in the selection of the fluid package of choice as any unsuitability would be
reflected in the obtainment of inaccurate simulation results.

Thus Peng-Robinson (PR) Equation Of State (EOS) was adopted as the preferred fluid
package. AspenTech recommended it for oil, gas and petrochemical applications due to its
special enhancement in HYSYS for the generation of accurate phase calculations over a wide
range of operating conditions (T > -271°C, P < 1000kPa). Our reaction conditions were well
within the range. Furthermore, literature values obtained for the reactor units had been based
primarily on the PR EOS.

The PSA was reflected as a component splitter in the PFD. PSA was a process unit
that could not be adequately simulated in Hysys, thus its simulation was performed in
COMSOL. The target specifications for the various major units had been met with the
convergence of the Hysys simulations, which also implied an overall satisfactory plant design.

1.3 REFERENCES

[R1]: Tom Gross. (2005). Hydrogen – An Overview. Foundation for Nuclear Studies Briefing.
[R2]: Wilhelm, D., Simbeck, D., Karp, A., Dickenson, R. (2001). Syngas production for gas-
to-liquids applications: technologies, issues and outlook. Fuel Proc. Tech., Vol 71 – P139
[R3]: Ferreira-Aparicio, P., Benito, M. J. & Sanz, J. L. (2005). New Trends in Reforming
Technologies: from Hydrogen Industrial Plants to Multifuel Microreformers. Catalysis
Reviews, 47:4, P491-588.
[R4]: Marshall Brain. How the Hydrogen Economy Works. Adapted on 15th Apr 2008 from:
http://auto.howstuffworks.com/hydrogen-economy.htm

Production of Hydrogen via Syngas Route 1-10


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design

Chapter 2 STEAM METHANE REFORMER


2.1 PROBLEM STATEMENT

2.1.1 Problem and Specifications

In this report, a Steam Methane Reformer (SMR) reactor unit is to be designed. The
plant is to produce hydrogen via the syngas route. The SMR reactor is one of the first units in
the process stream, and hence its design would be critical for the downstream process units,
in a bid to achieve an overall economical, safe and efficient plant for the hydrogen
production.

Amongst all, the design specifications for Team 32 are shown as follow:

• Location of Plant: Singapore


• Operation Time: 8000 hours / year
• Plant Capacity (PC): 1.25 × 109 m3(STP) / year
• Feed Composition (FC) to SMR reactor: 3 : 1 (H2O : CH4)
• % CO in H2 Specification at the exit of the shift converter: 0.7%
• Purity of hydrogen product: > 99.9% (mole)
• Natural Gas Feed: C1 = 97.7%; C2+ = 1.2%; CO2 = 0.7%; N2 = 0.4%

2.1.2 Justifications for using SMR

Justifications to leverage upon the SMR reactor unit for hydrogen production have been
found in literature. For instance, Wilhelm et. al. (2001) [R8] described the following
advantages, which are aligned with the current intention of the usage of the SMR unit. These
advantages have made SMR the chosen reforming concept. Hence, this project endeavours to
produce hydrogen via this syngas route.

 Lowest Tprocess required (better cost-savings)


 Extensive industrial experience
 Best ratio of H2 : CO for production applications of hydrogen
 Does not require O2 (cost-savings & safety enhanced)

Production of Hydrogen via Syngas Route 2-1


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.2 DESIGN METHODOLOGY & PROCESS DESIGN

2.2.1 Outline of Design Methodology

Fig 2.2.1a Flowchart to illustrate design methodology

2.2.2 Reaction Chemistries

CH4 + H2 O ↔ CO + 3 H2 Eqn (2-1)


CO + H2 O ↔ CO2 + H2 Eqn (2-2)
CH4 + 2 H2 O ↔ CO2 + 4 H2 Eqn (2-3)

3 governing equations responsible for the reactions in the reactor are given as above.
At this point, it is crucial to note that Beurden (2004) [R24] described that Eqn (2-3) is not a
combination of the Eqn (2-1) and Eqn (2-2) as CO2 is produced in both Eqn (2-2) and (2-3),
implying that the latter itself does not represent an overall reaction.

Production of Hydrogen via Syngas Route 2-2


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.2.2.1 Effects of Temperature and Pressure – Revisiting Le Chatelier’s Principle

La Chatlier’s Principles can be used to explain the effects of the operating conditions
for a typical SMR. A higher inlet temperature (typically 723 – 923K [R25]) would drive the
endothermic reactions (Eqn (2-1) & (2-3)) forward to produce more H2 product.

This is in contrast with that of the water-gas- shift (WGS) reaction (Eqn (2-2)), which
is favoured at lower temperature and not affected by pressure (same molar ratio on both sides
of reaction  no volume expansion).

Meanwhile, the stoichiometries of these 2 reforming reactions also suggested that


forward reactions are favoured when a lower pressure is used. This is to allow for volume
expansion to occur since the number of moles of product is greater than that of reactants.

2.2.2.2 Coke Formation, Steam:Methane ratio & Inclusion of CO2 in feed

Also, the Steam:Methane ratio (sc) used is 3. This coincides with what is typically
found in industrial practices, which suffice in suppressing coke formation [R24] during the
reaction. The presence of the carbon deposits during coke formation is detrimental to the
process as it would result in tube blockage, forming hot spots that can very well destroy the
tubes, threatening both the economics and safety of the process. Since this SMR reactor unit
design does not consider formation of coke, the choice of sc = 3 is made during the start of
the project to favour the design considerations of not involving coking as one of the reactions.

The suppression of coke formation is further promoted by the inclusion of CO2 [R25]
in the feed gas (Boudouard reaction during coking: 2CO = C + CO2), as mentioned in the
design brief. This shifts the Boudouard reaction backwards and thereby suppressing coke
formation. In addition, adding CO2 at the inlet of the reformer helps to save on hydrocarbon
feedstock and decrease the H2:CO formed in the SMR product stream. With these advantages
in mind, in industrial practice, some of these CO2 are typically being recycled from the SMR
product stream or being imported from another source.

Production of Hydrogen via Syngas Route 2-3


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.2.3 Choice of Reactor – Tubular Reformer

Nielsen (1993) indicated that the steam-reforming reaction typically involves catalysts
being loaded into tubes, which are in turn housed in a furnace to satisfy the highly endo-
thermic reaction. The tube material has to be capable to withstand the high temperature and
the temperature gradient (e.g. 1223 K at outlet [R25]).

As such, these tubular reactors typically experienced very huge stresses. Given that
upper limit of the tolerable stress value for the tubes is very much affected by the maximum
tube wall temperature and heat flux, a small rise in the maximum tube wall temperature could
very well resulting a reduction of life expectancy for these tubes.

Typical average lifespan of these reformer tubes can be around 100,000 hours. Given
that the current plant is designed to run at 8000 hours/yr, this would allow use for up to
a good 12.5 years. Such tubular reformer would be choice reactor for the current design
because it allows catalysts

Fig 2.2.3a: Typical Natural Gas & Reformer Catalysts. Retrieved from Midrex on World
Wide Web: http://www.midrex.com/uploads/documents/Catalyst(1)1.pdf

Production of Hydrogen via Syngas Route 2-4


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

Fig 2.2.3b: Tubular reformer configurations [R23, R25]

2.2.4 Justifications for Choice of Firing Configuration – Side-fired reformer furnace

The side-fired heating configuration is chosen because this has:

 Provided greater degree of control for Ttube wall to allow a more robust operation, to meet
the demands of the production by enduring more severe operating conditions. Also, a
higher average heat flux of 313800 kJ/h/m2 [R26] can be allowed.

 Shorter residence time discouraged [R25] formation of nitrogen oxides (NOx), up to


<50ppm, which is critical for the current design since it is assumed that no NOx is formed
in the SMR unit, even though there is presence of some N2 in the feed gas and that the
reactor is to be operating at high temperatures.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.2.5 Justifications for Choice of Fluid Package – Peng-Robinson

The Peng-Robinson fluid package is chosen because it gives a better prediction of


liquid densities than the Soave-Redlich-Kwong equation of state [R19]. In fact, the Peng-
Robinson equation of state is the most commonly used for systems containing non-polar
components [R20]. From the Table 2.2.4a below, it can be determined that Peng Robinson fluid
package remains the best choice as the system [R21].

Table 2.2.4a: Recommended


Property Package based on type
of system

2.2.6 Choice of Catalyst

Catalyst for steam reforming is typically nickel-based, which is cheaper than its noble
metal counterparts. Key criteria (besides costing) are to maximise activity and heat
transfer, while not causing a huge pressure drop. Non-metallic options are yet to be made
commercial because of the inherent low catalyst activity and thereby the impact of pyrolysis
[R27]
. The current work is based on that of Rajesh et. al. (2000) but there is no clear mention
of the catalyst used. Hence, the catalyst would follow that used by Xu and Froment (1989)
[R3,4]
, which is mentioned by Rajesh et. al, namely Ni/MgAl2O4. In this case, note that the
stability of the MgAl2O4 catalyst support is also very crucial in order to withstand conditions
during operation, start-up and shut-down [R27].

Production of Hydrogen via Syngas Route 2-6


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.2.7 Kinetics, Ni-based Catalyst & Role of Support

To facilitate the reforming reactions, the Ni-based catalyst is added to lower the
activation energies requirements. Intrinsic activity of the catalyst depends [R25] on the catalyst
surface available for chemisorption to occur. To do so, the cleavage of a C–H is needed, and
this entails overcoming the barrier of 52 kJ/mol and contacting a free Ni adsorbent site with
free neighbouring site. This chemisorption is of CH4 plays an instrumental role in
determining the reaction rates of the SMR process (typically given by CH4=CH3*  CH2*
 CH*=C*). Indeed, this is also aligned [R25] with the typical 1st order kinetics mentioned by
many [R2,3,4,5].

Nonetheless, as observed from Eqn (2-17) in Chapter 2.12.2.1, the presence of the
equilibrium adsorption constant for water (KH2O) may explain for a negative reaction order
with respect to the feed steam, giving rise to a ‘retarding effect’ whose extent may vary with
the choice of catalyst. In view of that, it is thus important to include alkali or use of magnesia
as support for the Ni catalyst, which provide for an enhanced level of adsorption of steam
molecules to avoid carbon formation.

2.2.8 Justification for Choice of Reactor Inlet Conditions

Rajesh et. al. (2000) [R1] suggested that inlet temperature for the SMR reactor should
not be lower than 725 K due to thermodynamic limitations, which thus prevent possible
formation of gum on the reformer catalyst. This would block the catalyst surface [R24] via
polymerisation of the adsorbed CnHm radicals. Such progressive deactivation is possible since
species like ethane (C2H6) is one of the components in the natural gas feed for the current
project. Meanwhile, operating at temperatures higher than 900 K is also not probable
because of the limitations for the maximum amount of heat energy that can be harnessed
form the flue gas. Meanwhile, it is also suggested [R1] that the inlet pressure is typically
between 2400 – 3000 kPa, after accounting for the normal pressures at which H2 is to be
produced, and the presence of natural gas as the feed. With these in mind, the arithmetic
averages for the inlet temperature and pressure (812.5 K and 2700 kPa) are used during the
detailed design of the SMR reactor unit.

Production of Hydrogen via Syngas Route 2-7


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.3 PRELIMINARY DESIGN

2.3.1 Establishment of Base Case

The governing reactions, key reactions and products for the reactor are first identified.
From the specified plant capacity provided in the design brief, and given the conversion
specified in literature (see trailing paragraph), a preliminary mass balance is then performed
across the reactor unit, after obtaining the SMR outlet flow rates from mass balance for the
inlet of trailing High Temperature Shift (HTS) unit. This gave an initial value for the flow
rates for the feed to be used.

Research efforts have been invested to find the conversion of the major component,
namely Methane (CH4). Coincidentally, for a Steam:Methane ratio of 3, Moulijn et. al. (2001)
[R9]
has reported on the expected methane slip is to be 21% (assuming P = 2700 kPa (27
bar); T = 1123.15 K), corresponding to a 79% (i.e. 100% - 21%) CH4 conversion.

Fig 2.3.1a: Literature data Moulijn et. al.


(2001) [R9] to support conversion obtained
during preliminary design is valid at the
assumed conditions (2700kPa & 1123.15K)

2.3.2 Preliminary Simulation using HYSYS

Initial efforts for SMR reactor design has been made via data from Hou & Hughes
(2001) [R6] literature data and using the Equilibrium Reactor module in HYSYS as a
simulation tool.

Production of Hydrogen via Syngas Route 2-8


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

Accordingly, the reactors were stainless steel tubes with 0.01m internal diameter and
0.338m long. Catalyst used was ICI steam reforming catalyst 57-4, which is of a cylindrical
fashion with 4 axial holes and provided by ICI Katalco. These catalysts have been crushed
prior to their usage. Amongst the various reaction equations given, the 3 predominant ones
haven seen selected and their respective equilibrium constants have been given.

Reaction Reaction Equilibrium Rate constant, Ki


1) CH4 + H2O = CO + 3H2 1.198 × 1017 exp(-26830/T) Eqn (2-4)
2) CO + H2O = CO2 + H2 1.767 × 10-2 exp(4400/T) Eqn (2-5)
3) CH4 + 2H2O = CO2 + 4H2 2.117 × 1015 exp(-22430/T) Eqn (2-6)
Table 2.3.2a: Reaction Equilibrium Rate constants, from Hou & Hughes (2001) [R6]

For a preliminary estimate, assume if TSMR, Exit = TSMR, Equilibrium = 1123.15K, then:
K1 = 5.058 × 106 (kPa)2; K2 = 8.884 × 10-1; K3 = 4.484 × 106 (kPa)2

With these Ki expressions, an Equilibrium Reactor module is specified in the


HYSYS Simulation Environment. Inlet pressure is assumed to be 270kPa (arithmetic average
of the TSMR, Inlet from the Rajesh et. al. [R1]), while inlet temperature is set to be 923.15K [R??].
Further research depicts an allowable pressure drop of 200 kPa [R27] may be typically used
across the SMR reactor unit. Overall, the simulation has achieved a CH4 conversion of ≈
79 mol%, which corresponds to that stipulated by the literature, as mentioned in
Chapter 2.3.1. The resultant process flow conditions are then presented in the interim report.
The latter would be used as an initial estimate for the respective downstream units.

Note: Streams and reactors data obtained at this stage from the HYSYS Process Flow
Diagram (PFD) via use of the Equilibrium Reactor) module merely provide initial iteration
values for solving of MATLAB Ordinary Differential Equations (O.D.E.s) for the detailed
design.

Production of Hydrogen via Syngas Route 2-9


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.4 DETAILED DESIGN

2.4.1 Development of Critical Profiles via MATLAB & Optimisation

To materialise the design of the reactor in detail, MATLAB is employed to solve for
the O.D.E.s given in literature [R1], after obtaining initial iteration values from the preliminary
design. The intention is to develop critical profiles and useful data via literature data and
assumptions, and fit the findings into the HYSYS Simulation Environment (using a PFR
module) for the overall plant design.

The MATLAB code developed could be found in the Appendix (Chapter 2.12.1). 2
m-files are written. The first one (Chapter 2.12.1.1) specified the reaction inlet conditions and
the tube dimensions, while using ode15s to resolve the O.D.E.s along the axial direction. The
second m-file (Chapter 2.12.1.2) specified the 4 O.D.E.s to be solved, as well as how each
parameter is obtained from literature.

Optimization is then performed by manipulating the various parameter like heat flux,
number of tubes and tube inner diameter being used. Since bulk of the written code followed
closely to the O.D.E.s developed by Rajesh et. al. (2000) [R1], the arithmetic averages for the
inlet pressure (2700 kPa) and temperature (812.5 K) of the range recommended by the same
journal are used to be the base case in this case.

2.4.2 Design Equations & Key Assumptions

Rajesh et. al. [R1] summarised the kinetic model and energy balance of the steam
reforming process, using a side-fired configuration with Mg-supported Ni catalyst. The 4
major O.D.E.s to be resolved via MATLAB are shown as follow.

dχ CH 4 πd i 2 Rη CH rCH
=( ) 4 4
; χ CH 4 =0 CH4 Differential Mass Balance Eqn (2-7)
dt 4 F t =0

dχ CO2 πdi 2 RηCO rCO


=( ) 2 2
; χCO2 =0 CO2 Differential Mass Balance Eqn (2-8)
dt 4 F t =0

dP 1.75G s (1 − catbedvoid ) Momentum Balance Eqn (2-9)


=− ; P t =0 = Pi
dt φ s D p (catbedvoid ) 3 ρ g

Production of Hydrogen via Syngas Route 2-10


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

dT 1  4H F 3

=  + ρ b ∑ ( − ∆H i )η i ri ) ; T t =0
= Ti Energy Balance Eqn (2-10)
dt Gmass Cp overall  d i i =1 

There 4 O.D.E.s have to be resolved to observe the profiles of how the CH4
conversion, CO2 conversion, pressure and temperature vary along the length of the reactor (t).
Expanded form of the expressions for the rates, effectiveness factors, adsorptions and rates
constants are available in Chapter 2.12.2.

Several key assumptions are made, including:

1) Constant heat flux <HF> is assumed, which implied [R28] that a well-controlled firing rate
is assumed. This is more probable [R27] in side-fired furnace used in this work due to
greater degree of adjustments and control over the tube wall temperature. Consensus is
also reached by Furnace Team to use a constant heat flux for the current work.
2) Effectiveness factor <ηi > for the ith reactions, which vary along the tube length, are fitted
with Excel, whose coefficients of the polynomial equations are then input into MATLAB.
3) There is negligible (0.001H2:1CH4) H2 recycle <hc> from the Pressure Swing Adsorption
(PSA) unit to the reformer feed.
4) Feed ratios <sc, dc & nc> and the total mass flow rate are obtained from HYSYS PFD.
The Adjust Function is used for more accurate values of the component molar flow rates.
5) No formation of NOx due to use of short flames of the side-fired furnace (Chapter 2.2.4).
6) No coking due to presence of CO2 in the reformer feed (Chapter 2.2.2).
7) N2 and higher carbons (C2+ = C2H6 in this work) remained inert in the SMR unit. Typical
compositions of Natural Gas feed may be found in Chapter 2.12.4 of the Appendix.
8) Catalyst dimensions and characteristics follow that of Rajesh et. al. (2000) [R1].
9) Density of process gas < ρ g > varies along the tube length <t>, which is taken to be the

division of the mass flow rate over volumetric flow rate.


10) Volumetric flow rate is taken to Molar flow rate × Universal gas cons tan t × Temperature
Pr essure

for any axial position <t>, hence Ideal Gas Law is assumed here.
11) For the MATLAB code being written, expressions for C2 is not available in the literature
used [R1], hence this is lumped the other inert species N2. However, in the HYSYS
Simulation, these two species are distinguished.

Production of Hydrogen via Syngas Route 2-11


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.4.3 Fitting into HYSYS Simulation Environment using Plug-Flow Reactor (PFR)

The HYSYS PFR module is employed to simulate the findings from MATLAB by:
1) Obtaining conditions of inlet and outlet streams, and also tubing and catalyst
specifications [R1,2,3,4] from optimisation in MATLAB, which are then fitted into the
HYSYS Simulation Environment.
2) Upon convergence in HYSYS, initial flow rates are then fitted back into MATLAB to re-
generate the critical profiles. These profiles are to be aligned with that in HYSYS.

As the flow fashion is now being modelled as plug flow [R7] in HYSYS, it is assumed
that no axial mixing occurs. This coincides with the intention of generating 1-D critical
profiles (with respect to Length of Reactor, t). Also, a Heterogeneous Catalytic reaction set
is chosen since the SMR reactor unit involves In the current HYSYS simulation, the PFR is
being segmented to 50, instead of the default value of 20. Hesketh (2003) [R7] described
that the increased number of steps conferred higher accuracy when resolving the O.D.E.s,
since now more steps used to resolve the O.D.E.s.

2.4.4 Results and Discussions

2.4.4.1 Conversion profiles for CH4 and CO2

Fig 2.4.4.1a:
Conversion
Profiles from
MATLAB

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

A desirable conversion of up to 80% is achieved for methane (CH4). This is in close


agreement with results obtained in the preliminary findings (Chapter 2.3.2), as well as that in
literature (Chapter 2.3.1). This also affirms that the SMR unit design is able to meet its
conversion targets for H2 production, as proposed in the interim report.

2.4.4.2 Temperature and Pressure Variations

Fig 2.4.4.2a: Pressure and Temperature profiles along length of reformer tube

Nielsen (1993) [R25] reported that typical outlet can be as high as 1223 K (9500C).
Hence, the current SMR exit temperature of 1100 K is still lower than the literature value.
As mentioned earlier in Chapter 2.2.3, it is noteworthy that neither very high temperature
nor great temperature gradient is encouraged since this may increase stress on the
reformer tubes, which greatly reduces the lifespan of the tubes.

Meanwhile, the pressure drop is about 65 kPa, which is lower than the proposed drop
of 200 kPa (2 bar) in the interim report. A lower pressure drop would mean that
downstream compressions could be avoided/minimised [R26], resulting in cost savings.

Production of Hydrogen via Syngas Route 2-13


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.4.4.3 Component Mole Fractions

Fig 2.4.4.3a: Component Mole Fractions from MATLAB

Fig 2.4.4.3b: Component Mole Fractions from HYSYS

Production of Hydrogen via Syngas Route 2-14


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

Comparing Fig 2.4.4.3a & b with


that of Fig 2.4.4.3c, it can be
observed that the simulated profiles
from both MATLAB and HYSYS
PFR are aligned with that in
literature by Rajesh et. al. (2001)
[R12]
on multi-objective optimization.
This may signified that the current
chosen design configuration has also
been optimized.

Fig 2.4.4.3c: Graph from literature


on mole fraction profiles [R12]

2.4.5 Optimization

Optimization has been performed to obtain the desirable reformer tube configuration
and operating conditions. At this juncture, since costs of the various materials (e.g. catalyst,
tube materials) are typically proprietary information, hence, the chosen tube dimensions and
the conditions of operation is based on other parameters. Through MATLAB, graphs of
increasing and
decreasing a
particular
parameter (e.g.
inner diameter, di)
are painstakingly
plotted. One
example is as
shown in Fig
2.4.5a.

Fig 2.4.5a: Effect of varying tubular inner diameter on CH4 conversion profile

Production of Hydrogen via Syngas Route 2-15


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

Fig 2.4.5b: Effect of varying pressure on CH4 conversion profile

Table 2.4.5a: Effect of Manipulating Parameters on Critical Profiles (from MATLAB)

As illustrated above, trends observed by increasing and decreasing selected


parameters are summarised in Table 2.4.5a. After several rounds of optimizing and fine
adjustments, the operating conditions and stream properties are presented in Chapter 2.4.6.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.4.6 Operating Conditions & Streams Conditions

Table 2.4.6a: Stream Properties & Operating Conditions (HYSYS PFR & MATLAB)

For overall integration purposes and in view that both HYSYS & MATLAB values
are in close agreement, these values from HYSYS are passed down to the downstream units.
Note that from HYSYS, a heating duty of 5.949 × 108 kJ/hr is required.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.5 MATERIALS OF CONSTRUCTION & SIZING

2.5.1 Selection Methodology

Selection of reactor materials has been made via the following considerations [R15].

• Conditions of exposure for reactor equipment being determined.


• Availability of materials being explored.
• Suitable material being identified.
• Ensured choice of material being substantiated with certifications.

The reactions involved exposed the SMR reactor unit to high temperature and
pressure. Comparisons between operating conditions for using MATLAB and HYSYS PFR
module revealed that these are typically as high as 1130 K (15750F) and 2700 kPa (391 psi)
[R16]
. In addition, there are chances of hot gas corrosion due to the high mass velocity.

2.5.2 Justifications for selecting from different grades of stainless steels

In view of these conditions, stainless steel is a suitable material for the construction of
these SMR reactor tubes, which can be summarised as such:

 Higher C Content  Offers greater creep resistance than other metals


 Addition of Ni and Cr  Resistance to carburization and creep being enhanced.

Different grades of heat resistance steel, namely, HH, HK, HD and HF. HK have been
specifically found to be of great use for SMR due to their high creep and rupture strength
even up to 1150°C. Most importantly, they offer resistance to hot gas corrosion. Literature
[R16]
revealed typical material of choice for SMR is HK40. Fig 2.5.2a illustrates the relative
tensile strengths of the different stainless steel grades.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

Fig 2.5.2a: Relative tensile strengths of different stainless steel grades

2.5.3 Tube life estimation, Minimum Stress Rupture & Identification of Choice Material

From Fig 2.5.3a [R16], at the high inlet pressure of 2700kPa (391 psi) and at the high
outlet temperature of 1130 K (1575 °F) for the reactor, the furnace tube life is found to
more than 20.3 years. This provides a confirmation that the material can be employed as
suitable for use in steam methane reforming processes.

Meanwhile, Fig 2.5.3b [R16] illustrates the minimum stress to rupture for the HK40
material as compared to other grades. The figure implies a lower performance of HK40 grade
compared to HP grades. However, since the maximum temperature is 1130 K, which is low
compared to the maximum temperature at which these stainless steel grades can withstand,
the pressure factor is taken for higher consideration in selection of the suitable metal type.
Since HK40 is capable of withstanding high pressure, HK40 would thus be chosen as the
choice of material for the reformer tubes (assuming economic considerations are ignored).

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

Fig 2.5.3a: Estimation of furnace tube life for a given set of operating temperature & pressure

Fig 2.5.3b: Minimum Stress to rupture for chosen material

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.5.4 Sizing – Computation for Tube Thickness

HK40 (25% Cr, 20% Ni) are usually used for steam reformer tubes [R16]. It has been
chosen for its high creep and rupture strengths. It is also resistant to hot gas corrosion and
hence is usually employed in steam methane reforming processes [R15]. Meanwhile, it
provides creep resistance up to 980°C (1253 K) [R17], making it a good candidate for the
current design whereby the highest temperature 856.85°C (1130 K). A standard code formula
is employed here to compute the minimum wall thickness required [R18], for sizing purpose
and specification of the PFR module in the HYSYS Simulation Environment.
d 
P i + FCA 
=  
min 2
t wall
S a E − 0.6 P
 0.1448 psi   0.127 m 1in 
 2700kPa × × × + 0.039in 
=
1kPa   2 0.0254m 
1000 psi 0.1448 psi
3.2ksi × × 0.85 + 0.6 × 2700kPa ×
1ksi 1kPa
0.0254m
= 0.399in ×
1in
−2
= 1.01 × 10 m
P = Max Pressure (to be in psig) = 2700 kPa (highest pressure at inlet);
di = Inner Diameter (to be in inches) = 0.127 m;
FCA = 10-year corrosion allowance (to be in inches) = 0.039 in [R18];
Sa = Minimum Creep Stress for HK40 (to be in psi) = 3.2 ksi;
E = Weld Efficiency Factor = 0.85 [R17].
Hence, a tube wall thickness of 1.01×10-2 m would be used.

2.5.5 Sizing – Summary

Inner Diamter (di) : 0.127 m (5”) Outer Diameter (do) : 0.147 m


Wall thickness : 0.0101 m No. of tubes needed : 450 (HK-40 Steel)

Further details of sizing of SMR reactor are to be done with Furnace unit counterpart
since these reformer tubes are housed in the furnace itself. These would then be presented in
the Final Team Report.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.6 ECONOMICS & SAFETY CONSIDERATIONS

2.6.1 Economic Analysis (Brief)

Table 2.6.1a: Costing Analysis for SMR unit [R29,30,31,32]

Due to lack of credible literature data to support the costing analysis, an extremely
rough estimate is given above in Table 2.6.1a. Computation efforts are done to illustrate how
costing analysis can be done if there is access to proprietary pricing information while
working as a real engineer. Nonetheless, further research effort would be done and cost
estimations (with other considerations) would be put forth in the Final Team Report.

2.6.2 Safety Consideration for Reactor Design

Reactor is the heart of the plant design. Given the high speed steam and natural gas to
be fed into the reactor, and the huge amount of heat is needed to supply to this endothermic
reforming process, a great deal of safety consideration has to be in place to ensure that the
plant and its operators can operate safety and efficiently.

In the Final Team Report where Process & Instrumentation analysis is done, more
findings on safety considerations would be reported, with collaborative efforts with the
furnace counterpart.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.7 LEARNING & CONCLUSIONS

In this report, the tubular reformer used for to produce hydrogen via a syngas route is
designed. Both preliminary and detailed design achieved similar conversions of the major
reactant component, namely Methane (CH4). Also, the detailed design is done via resolving
Ordinary Differential Equations in MATLAB by obtaining information from literature
research and making key assumptions with appropriate justifications. Besides, integration
into the team’s overall process flow diagram has also been done by inserting values from the
MATLAB model (which takes into account of both intrinsic kinetics and diffusional
limitations) into a Plug-Flow-Reactor module in the HYSYS Simulation Environment.
Results are considerably satisfactory since both values from MATLAB and HYSYS are in
close agreement with each other, and aligned with that found in literature. Meanwhile, tube
dimensions and material of constructions, brief economic analysis and safety considerations
have also been covered in this report

Several learning can be derived from the current work of design a Steam Methane
Reforming (SMR) reactor unit. Besides the need to plough through several literature data, the
author has learnt to exercise discretion when researching through the available information,
via perform the Principles of Chemical Engineering taught earlier.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.8 NOTATIONS

Sym. Description Units


th
Ki Equilibrium rate constant for i rxn K1 & K3: (kPa)2; K2: unitless
Kj Equilibrium adsorption constant for specie ‘j’ KCH4,H2,CO: (kPa)-1;
KH2O: unitless
T Temperature Kelvin (K)
P Pressure kPa
ki Rate constant for ith rxn k1,3: (kmol•kPa0.5)/(kg•h)
k2: (kmol•kPa-1)/(kg•h)
yj Mole Fraction for specie ‘j’ molj / moltotal
χj Conversion for specie ‘j’ j = CH4, CO2
sc Molar feed ratio of H2O:CH4 unitless
hc Molar feed ratio of H2(recycle stream):CH4 unitless
dc Molar Feed ratio of CO2:CH4 unitless
nc Molar Feed ratio of N2:CH4 unitless
ri Rate of ith rxn at catalyst surface kmol/(h•kgcat)
rj Rxn rate for specie ‘j’ at catalyst surface j = CH4, CO2; kmol/(h•kgcat)
ηi Effectiveness factor: ith rxn unitless
ηj Effectiveness factor: Conversion for jth specie j = CH4, CO2; unitless
Cpmean,i Mean Specific Heat Capacity of ith rxn kJ/(kmol•K)
Cpoverall Overall Specific Heat Capacity of ith rxn kJ/(kmol•K)
t Axial position in reformer tube m
di Inner diameter of reformer tube m
do Outer diameter of reformer tube m
catbedvoid Catalyst bed void fraction 0.605 [R1]
Gs Mass velocity of process gas (from HYSYS) kg/(h•m2)
Gmass Mass velocity of process gas (from HYSYS) kg/(s•m2)
φs Sphericity of catalyst pellet 0.6563 [R1]
Dp Equivalent length for catalyst pellet 0.0174131m [R1]
ρb Bulk density of catalyst 1362.0 kg/m3 [R1]
ρg Density of process gas at any axial position kg/m3 [R1]
F Reformer feed rate kmol/h
R Sum of all molar ratios in feed unitless
HF Heat Flux (= Heat Transfer Coefficient × Temp. kcal/(h•m2)
Diff b/w Tinner tube wall & Touter tube wall) Assume to be: 25000 Btu/h/ft2
or 283913.167 kJ/h/m2
th
- ∆H i Heat of the i reaction kcal/kmol
∆ H R ,i Heat of ith reaction kcal/kmol
υi Stoichiometric coefficient for ith reaction ‘-’  reactants;
‘+’  products

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.9 FIGURES AND TABLES

• Fig 2.2.1a Flowchart to illustrate design methodology


• Fig 2.2.3a: Typical Natural Gas & Reformer Catalysts
• Fig 2.2.3b: Tubular reformer configurations
• Table 2.2.4a: Recommended Property Package based on type of system
• Fig 2.3.1a: Literature data to support conversion obtained during preliminary design is
valid at the assumed conditions (2700kPa & 1123.15K)
• Table 2.3.1a: Reaction Equilibrium Rate constants, from Hou & Hughes (2001)
• Fig 2.4.4.1a: Conversion Profiles from MATLAB
• Fig 2.4.4.2a: Pressure and Temperature profiles along length of reformer tube
• Fig 2.4.4.3a: Component Mole Fractions from MATLAB Fig 4.4.3b: Component Mole
Fractions from HYSYS
• Fig 2.4.4.3c: Graph from literature on mole fraction profiles
• Fig 2.4.5a: Effect of varying tubular inner diameter on CH4 conversion profile
• Fig 2.4.5b: Effect of varying pressure on CH4 conversion profile
• Table 2.4.5a: Effect of Manipulating Parameters on Critical Profiles (from MATLAB)
• Table 2.4.6a: Stream Properties & Operating Conditions (HYSYS PFR & MATLAB)
• Fig 2.5.2a: Relative tensile strengths of different stainless steel grades
• Fig 2.5.3a: Estimation of furnace tube life for a given set of operating temp. & pressure
• Fig 2.5.3b: Minimum Stress to rupture for chosen material
• Table 2.6.1a: Costing Analysis for SMR unit

2.10 ACKNOWLEDGEMENTS

This section dedicates acknowledgements to all who have helped the author by
offering their valuable insights and advices. In particular, the author would like to express
gratitude to Prof. Kawi for his advice, as well as to Mr Thanneer for his consultation on the
MATLAB codes and functions. Last but not least, this work would not have been possibly
done without the coordination and teamwork in Team 32 (CN4120 – Sem 2 of AY2007/08),
hence the author would like to thank all of them for their assistance and understanding.

Production of Hydrogen via Syngas Route 2-25


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.11 REFERENCES

[R1]: J.K. Rajesh, Santosh K.Gupta, G.P.Rangaiah & Ajay K. Ray. (2000). Multiobjective
Optimization of Steam Reformer Performance Using Genetic Algorithm. Ind. Eng. Chen.
Res.: Vol 39 – P706-717.
[R2]: S.S.E.H. Elnashaie & S.S. Elshishini. (1993). Modelling, Simulation And Optimization
Of Industrial Fixed Bed Catalytic Reactors. Gordon And Breach Science Publishers.
[R3]: Jianguo Xu & Gilbert F. Froment (1989). Methane Steam Reforming, Methanation and
Water-Gas Shift: I. Instrinsic Kinetics. AIChE Journal: Vol 35 – No.1
[R4]: Jianguo Xu & Gilbert F. Froment (1989). Methane Steam Reforming: II. Diffusional
Limitations and Reactor Simulation. AIChE Journal: Vol 35 – No.1
[R5]: Kaihu Hou & Ronald Hughes. (2001). The kinetics of methane steam reforming over a
Ni/α-Al2O catalyst. Chemical Engineering Journal: Vol 82 – P311-328.
[R6]: Kaihu Hou & Ronald Hughes. (2001). The kinetics of methane steam reforming over a
Ni/α-Al2O catalyst. Chemical Engineering Journal.: Vol 82 – P311-328.
[R7]: Robert P. Hesketh. (2003). Catalytic Rates & Pressure Drops in PFR Reactors: HYSYS
3.0.
[R8]: Wilhelm, D., Simbeck, D., Karp, A., Dickenson, R. (2001). Syngas production for gas-
to-liquids applications: technologies, issues and outlook. Fuel Proc. Tech., Vol 71 – P139
[R9]: Moulijn, J., Makkee, M., van Diepen, A. (2001). Chemical Process Technology. John
Wiley & Sons Ltd (England).
[R10]: J.A. Moulijn, A.E. van Diepen & F. Kapteijn. (2001). Catalyst deactivation: is it
predictable? What to do? Applied Catalysis A: General 212 – P3-16.
[R11]: Chang Samuel Hsu & Paul R. Robinson. (2006). Practical Advances in Petroleum
Processing. Springer Science+Business Media, Inc.
[R12]: J. K. Rajesh, S. K. Gupta, G. P. Rangaiah & A. K. Ray. (2001). Multi-objective
optimization of industrial hydrogen plants. Chemical Engineering Science: Vol56–P999-1010.
[R13]: J.M. Smith, H.C. Van Ness & M. M. Abbott. (2005). Introduction to Chemical
Engineering Thermodynamics – 7th Edition. McGraw-Hill International Edition.
[R14]: Dilton, C.P. (1992). Materials selection for the chemical process industries. McGraw-
Hill.
[R15]: Retrieved on 16th March 2008 from World Wide Web:
http://www.valve-world.net/pdf/11022.pdf.

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

[R16]: V. Ganapathy. (1982). Applied heat transfer. PennWell.


[R17]: Retrieved on 10th March 2008 from World Wide Web:
http://www.fitness4service.com/publications/pdf_downloads/Jaske-Shannon%20Paper.PDF
[R18]: Retrieved on 18th March 2008 from World Wide Web:
http://www.kubotametal.com/alloys/heat_resistant/HK-40.pdf
[R19]: Retrieved on 18th March 2008 from World Wide Web:
http://www.tu-harburg.de/vt2/pe2000/Dokumentation/PE2000_Kap7A1.htm
[R20]: Chorng H. Twu, John E. Coon & David Bluck. (1997). A Comparison of the Peng-
Robinson and Soave-Redlich-Kwong. Equations of State Using a New Zero-Pressure-Based
Mixing Rule for the Prediction of High Pressure and High Temperature Phase Equilibria.
Simulation Sciences Inc.
[R21]: Retrieved on 17th March 2008 from World Wide Web:
http://che.sut.ac.ir/People%5CCourses%5C65%5CCHEM_2_3.PDF
[R22]: Retrieved on 10th March 2008 from World Wide Web:
http://encyclopedia.airliquide.com/Encyclopedia.asp?GasID=41
[R23]: Kelly Ibsen. (2006). Equipment Design and Cost Estimation for Small Modular
Biomass Systems, Synthesis Gas Cleanup, and Oxygen Separation Equipment. Nexant Inc.
[R24]: P. van Beurden. (2004). On the Catalytic Aspects Of Steam-Methane Reforming.
[R25]: J.R. Rostrup-Nielsen. (1993). Production of synthesis gas. Catalysis Today: Vol 18.
[R26]: Ib Dybkjaer. (1995). Tubular reforming and authothermal reforming of natural gas –
an overview of available processes. Fuel Processing Technology: Vol 42 – P85-101.
[R27]: H.I.deLasa, G.Dogu & A.Ravella. (1991). Chemical Reactor Technology for
Environmentally Safe Reactors and Products. Applied Sciences: NATO ASI Series Vol. 225
[R28]: J.R.Rostrup-Nielsenn, L.J.Christiansen & J.H.Bak Hansen. (1988). Activity of Steam
Reforming Catalysts: Role and Assessment. Applied Catalysis: Vol43–P287-303.
[R29]: Price of Nickel and Magnesium. Retrieved from World Wide Web on 19th March
2008: http://www.sciencelab.com/page/S/PVAR/10-807
[R30]: Price of HK-40 alloy (approximate): Retrieved from World Wide Web on 19th March
2008: http://www.meps.co.uk/Stainless%20Prices.htm
[R31]: Price of Al2O4: Retrieved from World Wide Web on 19th March 2008:
http://www.encyclopedia.com/doc/1G1-104622322.html
[R32]: Density of HK40 alloy: Retrieved from World Wide Web on 19th March 2008:
http://sg.search.yahoo.com/search?p=density+of+HK40+alloy&fr=yfp-t-
web&toggle=1&cop=&ei=UTF-8

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.12 APPENDIX

2.12.1 MATLAB Code

2.12.1.1 Main m-file to resolve O.D.E.s

clear all
clc
close all
format long
global catbedvoid phis Dp tube_length rhob rhos Pi Ti num_tubes_total di di_inch do
global Ac sc hc dc nc R
%SMR Inlet Conditions=================================================
Pi = 2700; %kPa; Inlet Pressure
Ti = 812.5; %K; Inlet Temperature; r/f [R1], this is b/w 725K and 900K
%Tubing Dimensions & Number===========================================
num_tubes_total = 450; %TOTAL number of tubes
di_inch = 5; %inch; Specify di in inches
di = di_inch*0.0254; %m; Inner tube diameter
Ac = pi*(di^2)/4; %m^2; Tube Cross-Sectional Area
tube_length = 11.95; %m; Length of tube
%Catalyst and Bed properties=============================================
Dp = 0.0174131; %m; Pellet equivalent diameter
catbedvoid = 0.605; %unitless; Catalyst bed void fraction
rhob = 1362.0; %kg/m^3; Catalyst bed density
rhos = 2355.2; %kg/m^3; Solid catalyst density
phis = 0.6563; %unitless; Pellet sphericity
%Molar Feed Compositions & Ratios=======================================
sc = 3; % steam/CH4 molar feed ratio ==> FIXED
hc = 0.0001; % H2/CH4 molar feed ratio; H2 from PSA RECYCLE
dc = 0.00716496; % mol.CO2 / mol.CH4; from HYSYS PFR
nc = 0.004094094; % mol.N2 / mol.CH4; from HYSYS PFR
%Specify conditions and solve for the 4 ODES=================================
tspan = [0 tube_length];
[t,y] = ode15s('smrodes',tspan,[0,0,Pi,Ti]);
%Simulation results====================================================
figure
subplot(2,2,1)
hold on
plot(t,y(:,1))
xlabel('Length of Reactor, m');
ylabel('CH4 conversion, xCH4');
subplot(2,2,2)
hold on
plot(t,y(:,2))
xlabel('Length of Reactor, m');
ylabel('CO2 conversion, xCO2');

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

subplot(2,2,3)
hold on
plot(t,y(:,3))
xlabel('Length of Reactor, m');
ylabel('Pressure, kPA');
subplot(2,2,4)
hold on
plot(t,y(:,4))
xlabel('Length of Reactor, m');
ylabel('Temperature, K');

2.12.1.2 Function m-file to define reactions conditions and O.D.E.s

function dy = smrodes(t,y)
% Only declare those used as CONSTANTS to be "global"
global R sc hc dc nc num_tubes_total Ac HF HF_btuperft2perhr do di di_inch rhob
catbedvoid phis Dp
global Fo FN2o FN2 G
global MWCH4 MWH2O MWH2 MWCO MWCO2 MWN2 MWC2H6 FN2 FN2o
global deltaA1 deltaB1 deltaC1 deltaD1
global deltaA2 deltaB2 deltaC2 deltaD2
global deltaA3 deltaB3 deltaC3 deltaD3
global H10 H20 H30
%These computations are done according to [R1], if there exists deviations,
%these would be typically be mentioned as comments.

%This m-file computes the 4 ODES to be resolved, whose solutions are then
%input in the matrix y, so as to resolve them al
xCH4 = y(1); %CH4 molar conversion at any axial position
xCO2 = y(2); %CO2 molar conversion at any axial position
P = y(3); %Pressure at any axial position
T = y(4); %Temperature at any axial position
%Computation for R===================================================
R = 1 + sc + hc + dc + nc; %sum of molar feed ratios
%Adsorption constants for Individual Species==============================
KCH4 = (6.65*10^(-6)).*exp(4604.28./T); %kPa^-1
KH2O = (1.77*10^(3)).*exp(-10666.35./T); %unitless; r/f [R1] & [R5]
KH2 = (6.12*10^(-11)).*exp(9971.13./T); %kPa^-1
KCO = (8.23*10^(-7)).*exp(8497.71./T); %kPa^-1
%Equilibrium constants for Rxn I, II & III================================
K1 = 10266.76.*exp(-26830./T + 30.11); %kPa^2
K2 = exp(4400.0./T - 4.063); %unitless
K3 = K1.*K2; %kPa^2
%Rate Coefficients for Rxn I, II & III====================================
k1 = 9.490*10^16.*exp(-28879./T); %kmol.kPa^0.5/kg.h
k2 = 4.390*10^4.*exp(-8074.3./T); %kmol.kPa^-1/kg.h
k3 = 2.290*10^16.*exp(-29336.0./T); %kmol.kPa^0.5/kg.h

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

%Effectiveness Factors for Rxn I, II & III================================


n1 = (-7*10^-7).*t.^6 + (3*10^-5).*t.^5 - 0.0004.*t.^4 + 0.0029.*t.^3 - 0.0102.*t.^2 +
0.015.*t + 0.0165;
%excel ==> deg 6
if (t <= 3.4)
n2 = -0.0059.*t.^5 + 0.0559.*t.^4 - 0.1971.*t.^3 + 0.3263.*t.^2 - 0.2316.*t + 0.0889;
%excel ==> deg 5
elseif (t == 3.4)
n2 = 0;
else
n2 = (-7*10^-6).*t.^4 + 0.0004.*t.^3 - 0.0074.*t.^2 + 0.0651.*t - 0.2158;
%excel ==> deg 6
end
n3 = (-6*10^-7).*t.^6 + (3*10^-5).*t.^5 - 0.0004.*t.^4 + 0.0033.*t.^3 - 0.0132.*t.^2 +
0.0229.*t + 0.0102;
%excel ==> deg 6

%GASEOUS Mole Fraction Basis for ALL SPECIES============================


yCH4 = (1-xCH4)./(R+2.*xCH4);
yH2O = (sc-xCH4-xCO2)./(R + 2.*xCH4);
yCO = (xCH4 - xCO2)./(R+2.*xCH4);
yCO2 = (dc + xCO2)./(R + 2.*xCH4);
yH2 = (hc + 3.*xCH4 + xCO2)./(R+2.*xCH4);
yN2 = nc./(R+2.*xCH4);
%Molecular Weights for ALL SPECIES=====================================
MWCH4 = 16.043; %kg/kmol; from [R2]
MWH2O = 18.01524; %kg/kmol; from [R2]
MWH2 = 2.016; %kg/kmol; from [R2]
MWCO = 28.01; %kg/kmol; from [R2]
MWCO2 = 44.01; %kg/kmol; from [R2]
MWN2 = 28.0134; %kg/kmol; from [R2]
%Flowrates (Mass & Molar); Density of Process Gas=========================
Fo = 1.040E4/num_tubes_total; % kmol/h
%Reformer Molar Feed Flow Rate at inlet for ONE TUBE; from HYSYS
FN2o = 10.4; % kmol(N2)/h
%yN2o * Fo = FN2o (for ONE TUBE) where yN2o is initial N2 mole fraction; from HYSYS
FN2 = FN2o; % kmol(N2)/h
%FN2o is the N2 molar flow rate at inlet = FN2 is the N2 molar flow rate at any axial length
F = FN2./(yN2*num_tubes_total); % kmol/h
%Total molar flow rate at any axial length for ONE TUBE
sv = ((F.*8.314.*T)./P)/(Ac); % m/h
%Superficial Velocity = Volumetric Flow Rate (ASSUME Ideal Gas) / Ac
G = 183287.978554998/num_tubes_total; % kg/h
%Total mass flow rate for ONE TUBE; from HYSYS
rhog = G./((F.*8.314.*T)./P); % kg/m^3;
%Density of gas mixture = Mass flow rate per tube / Volumetric Flow Rate per tube
Gmass = rhog.*sv; % kg/h/m^2; Mass velocity in per HOUR basis, to be used for dy(4)
Gs = Gmass/3600; % kg/s/m^2; mass velocity in per SECOND basis, to be used for dy(3)

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CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

%Rate of Rxns at catalyst surface at any axial position kmol/h/kgcat==================


E = 1 + P.*(KCO.*yCO + KCH4.*yCH4 + KH2.*yH2) + KH2O.*yH2O./yH2;
r1 = (k1./(E.^2.*yH2.^2.5.*P.^0.5)).*(yCH4.*yH2O-(P.^2.*yH2.^3.*yCO./K1));
r2 = ((k2.*P)./(E.^2.*yH2)).*((yCO.*yH2O)-((yH2.*yCO2)./K2));
r3 = (k3./(E.^2.*yH2.^3.5.*P.^0.5)).*(yCH4.*yH2O.^2-
(((yH2.^4.*yCO2).*(P.^2))./(K1.*K2)));
rCH4 = r1+r3; rCO2 = r2+r3;
nch4 = (n1.*r1 + n3.*r3)./(r1+r3); %effectiveness factor for adsorption of CH4
nco2 = (n2.*r2 + n3.*r3)./(r2+r3); %effectiveness factor for adsorption of CO2
%Specific Heat Capacities===============================================
%Compute constants to find Cp(mean) for Rxn I, II & III [R13]
%Recall Rxn1: CH4 + H2O = CO + 3H2
deltaA1 = (-1)*(1.702)+(-1)*(3.470)+(1)*(3.376)+(3)*(3.249);
deltaB1 = (-1)*(9.081/10^3)+(-1)*(1.450/10^3)+(1)*(0.557/10^3)+(3)*(0.422/10^3);
deltaC1 = (-1)*(-2.164/10^6) +(-1)*(0)+(1)*(0)+(3)*(0);
deltaD1 = (-1)*(0)+(-1)*(0.121/10^-5)+(1)*(-0.031/10^-5)+(3)*(0.083/10^-5);
%Recall Rxn2: CO + H2O = CO2 + H2
deltaA2 = (-1)*(3.376)+(-1)*(3.470)+(1)*(5.457)+(1)*(3.249);
deltaB2 = (-1)*(0.557/10^3)+(-1)*(1.450/10^3)+(1)*(1.045/10^3)+(1)*(0.422/10^3);
deltaC2 = (-1)*(0)+(-1)*(0)+(1)*(0)+(1)*(0);
deltaD2 = (-1)*(-0.031/10^-5)+(-1)*(0.121/10^-5) +(1)*(-1.157/10^-5) +(1)*(0.083/10^-5);
%Recall Rxn3: CH4 + 2H2O = CO2 + 4H2
deltaA3 = (-1)*(1.702)+(-2)*(3.470)+(1)*(5.457)+(4)*(3.249);
deltaB3 = (-1)*(9.081/10^3)+(-2)*(1.450/10^3)+(1)*(1.045/10^3)+(4)*(0.422/10^3);
deltaC3 = (-1)*(-2.164/10^6) +(-2)*(0)+(1)*(0)+(4)*(0);
deltaD3 = (-1)*(0)+(-2)*(0.121/10^-5) +(1)*(-1.157/10^-5) +(4)*(0.083/10^-5);
%Note that 1.987 is multiplied to convert kJ/mol.K to kcal/kmol.K
%Also, note that 298.15 K is reference temperature
%Also, T/298.15 is tile in [R13] Pg. 141 Eqn (4-20)
Cpmean1 = 1.987*(deltaA1 + (deltaB1/2)*(298.15).*(T/298.15+1) +
(deltaC1/3).*((298.15)^2).*((T/298.15).^2 + (T/298.15) + 1) +
deltaD1./((T/298.15).*298.15^2));
Cpmean2 = 1.987*(deltaA2 + (deltaB2/2)*(298.15).*(T/298.15+1) +
(deltaC2/3).*((298.15)^2).*((T/298.15).^2 + (T/298.15) + 1) +
deltaD2./((T/298.15).*298.15^2));
Cpmean3 = 1.987*(deltaA3 + (deltaB3/2)*(298.15).*(T/298.15+1) +
(deltaC3/3).*((298.15)^2).*((T/298.15).^2 + (T/298.15) + 1) +
deltaD3./((T/298.15).*298.15^2));
%Note that divide by 4.196 such that kJ/kmol ==> kcal/kmol
H10 = (2.061*10^5) /(4.186); %ENDOTHERMIC; [R1]
H20 = (-4.11*10^4) /(4.186); %EXOTHERMIC; [R1]
H30 = (1.650*10^5) /(4.186); %ENDOTHERMIC; [R1]
%Heats of Reactions===================================================
H1 = H10 + Cpmean1.*(T-298.15); %kcal/kmol
H2 = H20 + Cpmean2.*(T-298.15); %kcal/kmol
if (n2<0)
H2 = -H2; %kcal/kmol
else
H2 = H2; %kcal/kmol
end

Production of Hydrogen via Syngas Route 2-31


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

H3 = H30 + Cpmean3.*(T-298.15); %kcal/kmol


sum1 = -H1.*n1.*r1; %for dy(4)
sum2 = -H2.*n2.*r2; %for dy(4)
sum3 = -H3.*n3.*r3; %for dy(4)
%Heat Flux (CONSTAN VALUE IS ASSUMED HERE; r/f to Chapter 2.4.2 for explanation)
HF_btuperft2perhr = 25000; %btu/h/ft^2; from [R11]
HF = HF_btuperft2perhr*2.71427502; %kcal/h/m^2;
%Weight Fraction for ALL SPECIES=======================================
%From ABOVE ==> G is Total mass flow rate for ONE TUBE; from HYSYS
wCH4 = (yCH4.*F)*MWCH4./G;
wH2O = (yH2O.*F)*MWH2O./G;
wH2 = (yH2.*F)*MWH2./G;
wCO = (yCO.*F)*MWCO./G;
wCO2 = (yCO2.*F)*MWCO2./G;
wN2 = (yN2.*F)*MWN2./G;
%Specific Heat Capacities for ALL SPECIES=================================
CpCH4 = 1.987*(1.702 + (9.081/10^3).*T + (-2.164/10^6).*T.^2 + (0).*T.^-
2)/MWCH4; %kcal/kg.K
CpH2O = 1.987*(3.470 + (1.45/10^3).*T + (0/10^6).*(T.^2) + (0.121/10^-
5).*(T.^-2))/MWH2O; %kcal/kg.K
CpH2 = 1.987*(3.249 + (0.422/10^3).*T + (0/10^6).*(T.^2) + (0.083/10^-5).*(T.^-
2))/MWH2; %kcal/kg.K
CpCO = 1.987*(3.376 + (0.557/10^3).*T + (0/10^6).*(T.^2) + (-0.031/10^-
5).*(T.^-2))/MWCO; %kcal/kg.K
CpCO2 = 1.987*(5.457 + (1.045/10^3).*T + (0/10^6).*(T.^2) + (-1.157/10^-
5).*(T.^-2))/MWCO2; %kcal/kg.K
CpN2 = 1.987*(3.280 + (0.593/10^3).*T + (0/10^6).*(T.^2) + (0.040/10^-5).*(T.^-
2))/MWN2; %kcal/kg.K
Cpoverall = wCH4.*CpCH4 + wH2O.*CpH2O + wH2.*CpH2 + wCO.*CpCO +
wCO2.*CpCO2 + wN2.*CpN2; %kcal/kg.K
%Ordinary Differential Equations==========================================
dy(1) = Ac.*R.*rhob.*nch4.*rCH4./Fo;
dy(2) = Ac.*R.*rhob.*nco2.*rCO2./Fo;
dy(3) = -(1.75*(Gs^2)*(1-catbedvoid))./(phis*Dp*((catbedvoid)^3).*rhog)/1000;
%/1000 is to account to change Pa to kPa so as to use P for other functions
dy(4) = (1./(Gmass.*Cpoverall)).*((4*HF)/di + rhob.*(sum1+sum2+sum3));
% note that units for Cpoverall is kcal/kg.K
dy = dy';

%Note: This is skeletal MATLAB developed to solve for the 4 O.D.E.s. Additional strings of
code used to generate the various plots shown in Chapter 2.4.4, 2.4.5 and 2.4.6 are not shown
here due to space constraint. In general, just need to comment off the ‘clear all’ command,
and then vary the parameter(s) (e.g. num_tubes_total), and record the figures in a new matrix
after each run. Thus, graphs with different num_tubes_total can then be plotted on one plot.

Production of Hydrogen via Syngas Route 2-32


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.12.2 List of Equations

2.12.2.1 Rate Equations for reactions and species for 4 O.D.E.s

3
k1 P 2 y H 2 y CO kmol
r1 = ( y CH 4 y H 2O − ); Eqn (12-11)
2
E yH2 P
2.5 0.5
K1 h • kg cat

k2 y H y CO2 kmol
r2 = ( y CO y H 2O − 2 ); Eqn (12-12)
2
E yH2 K2 h • kg cat
4
k3 2 y H 2 y CO2 P 2 kmol
r3 = ( y CH 4 y H 2O − ); Eqn (12-13)
2
E yH2 P
3.5 0.5
K3 h • kg cat

rCH 4 = r1 + r 3 Eqn (2-14) rCO2 = r2 + r 3 Eqn (2-15)

R = 1 + sc + hc + dc + nc (used in Eqn (4-1) & (4-2)) Eqn (2-16)


y H 2O
E = 1 + P( K CO yCO + K CH 4 yCH 4 + K H 2 yH 2 ) + K H 2 O Eqn (2-17)
yH2

2.12.2.2 Mole Fractions for species

1 − χ CH 4 sc − χ CH 4 − χ CO2
yCH 4 = Eqn (2-18) y H 2O = Eqn (2-19)
R + 2 χ CH 4 R + 2 χ CH 4

χ CH − χ CO dc + χ CO2
yCO = 4 2
Eqn (2-20) yCO2 = Eqn (2-21)
R + 2 χ CH 4
R + 2 χ CH 4

hc + 3χ CH 4 + χ CO2 nc
yH2 = Eqn (2-22) y N2 = Eqn (2-23)
R + 2 χ CH 4 R + 2 χ CH 4

2.12.2.3 Effectiveness Factors for reactions and species

η1 , η 2 & η 3 are obtained via fitting polynomials using Microsoft Excel. Points are
specified via identifications of coordinates for these 3 curves via vigorous read-off.
η1 = ( −7 × 10 −7 )t 6 + (3 × 10 −5 )t 5 − (0.0004)t 4 + (0.0029)t 3 − (0.0102)t 2 + 0.015t + 0.0165
Polynomial of degree 6 Eqn (2-24)
η 2 = (−0.0059)t 5 + (0.0559)t 4 − (0.1971)t 3 − (0.3263)t 2 + 0.2316t + 0.0889
Polynomial of degree 5 (for t < 3.4) Eqn (2-25)

Production of Hydrogen via Syngas Route 2-33


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

η 2 = (−7 × 10 −6 )t 4 + (0.0004)t 3 − (0.0074)t 2 + 0.0651t − 0.0.2158


Polynomial of degree 4 (for t =3.4 and t > 3.4) Eqn (2-26)
η 3 = ( −6 × 10 −7 )t 6 + (3 × 10 −5 )t 5 − (0.0004)t 4 + (0.0033)t 3 − (0.0132)t 2 + 0.0229t + 0.0102
Polynomial of degree 6 Eqn (2-27)
η1 r1 + η 3 r3
η CH = Eqn (2-28)
4
r1 + r3

η 2 r2 + η 3 r3
η CO = Eqn (2-29)
2
r2 + r3

2.12.2.4 Rate & Adsorption constants for reactions 1, 2 and 3

 − 28879 .0  kmol • kPa


0 .5
k1 = 9.490 × 10 6 exp ; Eqn (2-30)
 T  kg • h
−1
 − 8074 .3  kmol • kPa
k 2 = 4.390 × 10 4 exp ; Eqn (2-31)
 T  kg • h

 − 29336 .0  kmol • kPa


0 .5
k 3 = 2.290 × 10 16 exp ; Eqn (2-32)
 T  kg • h

 − (26830.0) 
K 1 = 10266.76 exp + 30.11; kPa 2 Eqn (2-33)
 T 
 − (−4400.0) 
K 2 = exp − 4.063 ; unitless Eqn (2-34)
 T 
K 3 = K 1 × K 2 ; kPa 2 Eqn (2-35)

2.12.2.5 Adsorption constants for species

 − ( −4604.28) 
K CH 4 = 6.65 × 10 −6 exp ; kPa
−1
Eqn (2-36)
 T 
 − (10666.35) 
K H 2O = 1.77 × 10 3 exp ; unitless Eqn (2-37)
 T 
 − ( −9971.13) 
K H 2 = 6.12 × 10 −11 exp ; kPa
−1
Eqn (2-38)
 T 
 − ( −8497 .71) 
K CO = 8.23 × 10 −7 exp ; kPa
−1
Eqn (2-39)
 T 

Production of Hydrogen via Syngas Route 2-34


CN 4120: Design II
Team 32: Lim Yueh Yang (U046787U) SMR Unit Design Report

2.12.2.6 Heat Capacities

∆H i = ∆H R ,i + Cp mean ,i (T − TR ) Eqn (2-40)

 
 2 
(υ B )T  T  (υ C )(T )  T  T
2
 (υ D ) 
Cpmean , i = R (υi Ai ) + i i 0  − 1 + i i 0    + + 1 + i i 
   T0  T0  T
2  T0  3
  (T0 )2 
 T0 

Values of A, B, C and C for the respective species for the ith reaction are found in [R13].
Eqn (2-40)

2.12.3 Sample Calculations

Most of the calculations are performed via MATLAB and the HYSYS Simulation
Environment, so long as the relevant parameters are specified. Hence, sample calculations
would not be shown in this work. All the MATLAB written have comment statements
intended to make the code self-explanatory.

2.12.4 Typical Natural Gas Compositions

Figure is retrieved from Midrex from World Wide Web on 19th March 2008 at:
http://www.midrex.com/uploads/documents/Catalyst(1)1.pdf.

Production of Hydrogen via Syngas Route 2-35


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

Chapter 3 : FURNACE
3.1 INTRODUCTION

3.1.1 Furnace design methodology

Furnaces serve various purposes in process industries such as column reboilers,


reactor-feed preheaters etc. Unlike typical furnaces; the furnace used for the steam methane
reforming has additional design considerations compared to conventional furnaces. The
furnace in this project is used to provide energy for the steam methane reaction. It provides
single-phase/multiple-component heating. In addition, the convection section of the furnace
serves to extract excess heat from the flue gas to heat up process streams from other part of
the plant. Typically, 70% of the heat generated by the burner goes to the radiation section
while the remaining 30% goes to the convection. Single phase multiple components heating
will be carried out by the furnace. Catalysts would be placed in the reactor tubes lining the
refractory.
The furnace design would incorporate the following considerations:
(1) Capacity and size of furnace (2) Dimensions of reactor tubes
(3) Material selection (4) Safety considerations

Fig 3.1.1a: Furnace design methodology

Production of Hydrogen via Syngas Route 3-1


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.1.2 Heat transfer process in fired heater

There are two main heat transfer process – radiation and convection. Radiation occurs
within the radiation zone where fire from the burners heats up the tubes containing the
process fluid, in this case the reactants and products of the steam methane reform reaction. In
the convection zone, heat transfer is a combination of non-luminous and convective heat
transfer. The flue gas is the main medium for convective heat transfer to take place.

3.2 RADIATION ZONE DESIGN

Heat transfer to the radiant zone is the most important aspect of design for a fired
heater. An acceptable heat flux and metal tube temperature has to be achieved during design4.

3.2.1 Thermal Efficiency of Fired Heater

Heater efficiency is essential for determining the energy to be supplied through the
combustion process in the fired heater. It is the ratio of the amount of heat transferred to the
tubes to the amount of heat generated through combustion in the fired heater. The heater’s
efficiency is dependent on the following factors:
• Flue-gas stack temperature
• Excess air or oxygen
• Heat lost to the surrounding
• Design of the convection section in the fired heater

The flue gas stack temperature can be computed using the approach temperature,
which is the difference in the stack temperature to the inlet fuel temperature. Typical
approach temperature varies between 100-150°F1. Through HYSYS simulation, the stack gas
temperature is 565.6°C. The percentage heat available (thermal efficiency) can be derived
from the graph as shown below. Typically, heat efficiency can also be computed from the
following equation:
Heat available at flue gas temperature
Heater Efficiency =
Lower Heating Value of fuel gas

Production of Hydrogen via Syngas Route 3-2


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

To obtain the furnace efficiency, a theoretical flame temperature has to be found.


However, a few assumptions have to be made to simplify calculations.
• Combustion of nitrogen is negligible • No carbon monoxide is formed

To calculate the heat released from combustion and the temperature of the products
formed, the enthalpy change of the combustion process can be considered2.

Fig 3.2.1a: Thermodynamic flow of combustion reaction


The total heat of combustion can be given as  Heat of combustion = ∆HR + ∆HP + ∆H0C
Assuming adiabatic combustion, heat of combustion = 0  ∆HP = -∆HR - ∆H0C

Composition of fuel gas from PSA outlet consists mainly of CH4 and H2 where
number of moles of H2 is 3 times the number of moles of CH4. The other components will be
ignored for furnace efficiency computations as they are present in small quantities.

Hence, the main combustion reactions considered for calculations are


(1) CH4 + 2O2 → CO2 + 2H2O (2) 2H2 + O2 → 2H2O

Production of Hydrogen via Syngas Route 3-3


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

Hence, Number of Moles of


CH4= 1; H2 = 3; O2 = 3.5; CO2 = 1; H2O = 5; N2 = (0.79/0.21) x 3.5 = 13.17

To compute ∆HR, assume


• Temperature of air is preheated to 150°C and
• Temperature of fuel feed from PSA unit is 40°C
• Flame temperature is 1900°C
• 1 mol of CH4 present
• Air comprise of 79% N2 and 21% O2

The Cp of the gases present at a flame temperature is obtained from literature.


Using the table above and with excel spreadsheet, iteration is performed to obtain the flame
temperature. A flame temperature is first assumed.
No. of moles % excess air Cp (KJ/mol-K)
Reactant Fuel CH4 1 68.05
H2 3 30.5
Air O2 3.5 1.15 34.25
N2 13.16666667 1.15 32.39
Product CO2 1 52.31
H2O 5 40.93
N2 13.16666667 1.15 32.39
O2 3.5 0.15 34.25
Table 2.1a: Excel spreadsheet used in calculation for flame temperature

∆HR = (68.05+3 x30.5) (50-25) + (34.25 x 3.5 x 1.15 + 13.17 x 1.15 x 32.39) (150-25) =
82525 KJ/mol
∆HP = (1 x 52.31 + 5 x 40.93 + 13.17 x 1.15 x 32.39 +3.5 x 0.15 x 34.25) x (flame T – 25) =
765.4 (flame T -25)
∆H0C can be computed as: ∆H0C = 802800 + 241800 = 1044600 KJ/mol

Hence, 765.4 (flame T -25) = 1044600 – 82525  Flame T = 1389°C

Production of Hydrogen via Syngas Route 3-4


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

The flame T is quite close to the original flame temperature calculated and hence flame T will
be taken to be 1390°C.

Fig 2.1: Flue gas profile of fired heater

Given the furnace profile: Furnace Effficiency = (Heat to process) / (Heat released by fuel)

Assuming stack temperature is 150°C,


Furnace efficiency = 765.4 (1390 -150) / (1044600 – 80930) = 0.9449

As it is usually not an adiabatic combustion process, heat is also lost to the


surrounding through the refractory walls. The value of heat loss is usually 2%3. Hence, the
overall thermal efficiency of the furnace is: 94.49 – 2 = 92.49%

Calculating the amount of heat to be supplied by the furnace, based on the energy
requirement specified by the SMR personnel,

100
Energy required = × 5.97 × 10 8 = 6.45 x 108 KJ/h.
92.49

Assuming purged product from PSA contain a majority of methane gas for
combustion, the LHV of the fuel feed to the furnace will be approximately 50MJ/kg (5 x 104
5.82 × 10 8
KJ/kg). Hence amount of fuel feed needed is = = 1.29 x 104 kg/h.
5 × 10 4

Production of Hydrogen via Syngas Route 3-5


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

Given simulation from HYSYS, amount of PSA outlet is approximately 1 x 105 kg/h.
Since the CH4 content is not exactly 100%, despite the excess in quantity of fuel from PSA
outlet to that required, the totally energy that can be supplied will be the same as that of a
pure methane feed of lower quantity. Hence, the amount of fuel supplied from PSA outlet is
sufficient for supporting furnace combustion. However, in case insufficient fuel is supplied
from the PSA outlet due to equipment fault, a makeup fuel feed will be fed to the furnace.
This will be done through control instrumentation design. The amount of makeup feed will
then be 1.163 x 104 kg/h.
Fig 3.2.1d: Suggested
instrumentation control
for fuel gas inlet
control

3.2.2 Calculation for the number of reformer tubes

The number of reactor tubes within the furnace can be computed from an average heat
flux. Typical heat flux value for reformer unit is3 25000 BTU/h-ft2. With the number of tubes
computed, the mass velocity within the reformer tubes can then be computed. An excel
spreadsheet was used to compute the number of tubes from the heat flux value. The value of
heat flux is found in literature6 to be 25 000 BTU/hr-ft2.

Production of Hydrogen via Syngas Route 3-6


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

Length of tube (ft) 39.2


Internal diameter of pipe (ft) 0.417
Surface area of tube (ft2) 51.3277
Total energy required in KJ/h as derived from HYSYS 5.97 x 108
Average flux in KJ/hr-ft2 as specified in literature 25000
No. of tubes 465
Table 3.2.2a: Computation for no. of tubes with heat flux
The number of tubes was calculated using the following equation:
Total energy required as derived ( HYSYS )
= Average heat flux (literature)
π × Internal diameter of pipe × length of tube

Hence it can be concluded that the number of tubes to be used for the reactor is
approximately 465 tubes. However, since the SMR personnel have obtained good conversion
with 450 tubes, 450 tubes will be used for further design considerations.

3.2.3 Calculation for mass velocity in reformer tubes

total mass flow of reac tan ts


Mass velocity ( per reformer tube) =
no. of tubes × cross sec tion per tube
Total SMR feed load (kg/h) 182400
Total SMR feed load (lb/s) 111.4667
Internal diameter of pipe (inches) 5
Internal diameter of pipe (ft) 0.417
cross section of pipe in (ft2) 0.0137
mass flow velocity in lb/s (ft2) 18
No. of tubes 450
Table 3.2.3a: Computation for no. of tubes from mass velocity

The mass velocity of the fluid in the tube can be found to be around 18 lb/s ft2. The
minimum mass flow velocity required of 15 lb/s ft2 is satisfied.

Production of Hydrogen via Syngas Route 3-7


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

Turndown consideration

It is important to consider turn-down and possible stream recycling. Usually,


turndown of 60%16 is taken into account. 60% x 15 = 10.8 lb/s ft2.

However, as the furnace supports a reaction process, recycling will not be considered.

3.2.4 Calculation of reformer tube thickness

HK40 (25% Cr, 20% Ni) are usually used for steam reformer tubes4. HK40 is chosen
for its high creep and rupture strengths. It is also resistant to hot gas corrosion and hence is
usually employed in steam methane reforming processes5. It provides creep resistance up to
980°C. This makes it suitable for the current design where the highest temperature 826.85°C6.
A standard code formula is employed to calculate the minimum wall thickness required7.

d   0.1448 psi   0.127m 1in 


P i + FCA   2700kPa × × × + 0.039in 
=  = 
min 2 1kPa   2 0.0254m  = 0.399in
t wall
S a E − 0.6 P 1000 psi 0.1448 psi
3.2ksi × × 0.85 + 0.6 × 2700kPa ×
1ksi 1kPa

P = Max Pressure (to be in psig) = 2700 kPa (highest pressure at inlet);


di = Inner Diameter (to be in inches) = 0.127 m;
FCA7 = 10-year corrosion allowance (to be in inches) = 0.039 in;
Sa7 = Minimum Creep Stress for HK40 (to be in psi) = 3.2 ksi;
E 6 = Weld Efficiency Factor = 0.85.

Production of Hydrogen via Syngas Route 3-8


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.2.5 Selection of material for reactor tube in radiation section

A series of procedure has been developed to aid the selection of material for reactors8.
1. Define the conditions of exposure (eg. Temperature and pressure)

2. Explore available materials

3. Identify the suitable material

4. Evaluate the material

In the steam methane reforming process, the reactor will be exposed to high
temperature of approximately 1130K and pressure of 2700kPa9. In addition, there are chances
of hot gas corrosion due to the high mass velocity. In view of these conditions, stainless steel
is a suitable material for the construction of the steam methane reformer tubes. With higher
carbon content, stainless steel offers greater creep resistance than other metals. With the
addition of nickel and chromium, resistance to carburization and creep is enhanced. There are
different grades of heat resistance steel, namely, HH, HK, HD and HF. HK has been
specifically found to be of great use in steam methane reforming due to their high creep and
rupture strength even up to 1150°C.

Most importantly, it
offers resistance to
hot gas corrosion.
The following figure
shows the superiority
of HK40 metal
compared to other
grades. It shows the
relative tensile
strength of the
different stainless
steel grades.

Fig 3.2.5a: Tensile strength

Production of Hydrogen via Syngas Route 3-9


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

In addition, the tube life can be determined as follows.

Fig 3.2.5b: Tube life of HK40 tube

From the figure, at pressure of 2700kPa (391psi) and temperature of 1130K, the
furnace tube life can be found to be more than 20.3 years. This provides a confirmation that
the material is suitable for use in steam methane reforming processes.

The follow figure shows the minimum stress to rupture for HK40 piping as compared
to other grades. The figure implies a lower performance of HK40 grade compared to HP
grades. However, since the maximum temperature is 1130K, which is low compared to the
maximum temperature at which these
stainless steel grades can withstand, the
pressure factor is taken for higher
consideration in selection of the suitable
metal type. Since HK40 is capable of
withstanding higher pressure, will be the
final choice of material for the reformer
tubes.

Fig 3.2.5c: Minimum stress Vs Temperature

Production of Hydrogen via Syngas Route 3-10


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.2.6 Reformer inner tube diameter

Tube sizes ranging from 4 to 8 inches are usually used based on the standard nominal
pipe size. A 5 inch inner tube diameter has been chosen based on the tube thickness
calculated (0.399 inches) and the standard nominal tube sizes1. Hence a Schedule 8016 tube
constructed from HK40 stainless steel will be used for the reformer tubes.

3.2.7 Furnace layout and design

3.2.7.1 Side Fired Heater

A side fired heater with vertical tubes has been used for simulation of the SMR
reaction. Hence, a side fired heater design will be proposed for the furnace type.

Side fired furnace has a few advantages. It allows the adjustment and control of the
tube wall temperature. The maximum temperature will be at the outlet of the reformer tube
while the highest heat flux is at a relatively low temperature. The side fired furnace offers
more flexibility in design and operation10. Side fired configuration also allows a counter-
current flow of flue gas and process fluid which yields a higher heater efficiency.

A typical side fired heater has the following configuration as found


in literature10.

However, given the large number of tubes, it is not economically feasible to line the
tubes in two rows as a large amount of space will be needed. Hence, 4 rows of tubes will be
proposed, each row comprising 450 /4 = 112 or 113 tubes.

Production of Hydrogen via Syngas Route 3-11


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.2.7.2 Distance between burners

The distance
between the burners
is kept at 4m. This is
to ensure a safe
distance between the
tubes and the two
burners. The 2-D
sketch is shown
below.

Fig 3.2.7.2a: Proposed side-fired heater design (radiation + convection zone)

Given the tube dimensions as computed and that tube pitch is taken as twice the tube
outer diameter, and taking the allowance from the refractory wall to be 1 m in total,
Tube dimensions
Length (m) 11.95
I.D (m) 0.127
O.D (m) 0.147
Number of tubes per row 113
Tube pitch (where D =
outer diameter) 2 x O.D

Length of furnace
= No. of tubes per rows × Tube pitch × Outer diameter per tube
+ Allowance
Hence length of furnace is approximately 33m.

Production of Hydrogen via Syngas Route 3-12


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

The pigtails will be approximated to be 0.5m each. Pigtails are used to allow
expansion and contraction of tubes during start up. It minimises the need for joints and
welding that may fail when there is too much stress. Inlet pigtails are silicon killed while
outlet pigtail is made up of high alloy material.

Height of the radiant section will be taken to be: 11.95m + length of pigtails = 13m.

A 3-dimensional proposed design is as shown below.

Fig 3.2.7.2a: 3-D view radiation zone of proposed side-fired heater

3.2.7.3 Burners used at Side Walls

Premix burners will be used for the side wall. This is because they offer better
linearity, where excess air remains more nearly constant at turndown. Air will be drawn in
through the primary box register and mixed with the fuel before it flows to the furnace
firebox. Good mixing has to be ensured so that a short non-yellow flame can be obtained.
This is to prevent the flame from being in contact with the reformer tubes and cause locus
increase of temperature on the reformer tube. Long flames cause tube failure in the long run
and soot blower may be necessary to clean the heating surface. The figure below shows a
typical premix burner11.

Production of Hydrogen via Syngas Route 3-13


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

Fig 3.2.7.3a: Pre-mix burner

However, usually gaseous fuels provide non-luminous flames4.

3.2.7.4 Determination of number of burners

The length of the furnace box is given to be 33m. For maximum heat distribution, the
centre to centre distance between burners should be 1m. Hence there would be approximately
32 burners along the length of the furnace. Since the height of the furnace is 13m, the number
of burners along the height of the furnace is 12. The layout on the refractory wall is shown
below. The total number of burners used will be 3072 burners.

Fig 2.7.4a: Side-fired heater burner arrangement

Production of Hydrogen via Syngas Route 3-14


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.2.8 Computations for flue gas temperature

The flue gas temperature as obtained from HYSYS is 565.6°C. However, the
conversion reactor is used in the HYSYS design, which is a steady state module. Hence, more
calculations should be done to clarify the flue gas temperature. These set of calculations take
into account the dynamic state of the furnace.

3.2.8.1 Cold plane area

The cold plane area, which is the projected area of reformer tubes, is calculated as
follows13:

Acp= exposed tube length x centre to centre spacing x number of tubes excluding shield tubes.
= 11.95 x 2 (pitch) x 0.147 (outer diameter of pipe) x 450 = 1584 m2.

3.2.8.2 Refractory area

The refractory area is defined as the inside surface of the shell minus the cold plane
area. The equation for computation of the refractory area is as follows:
Aw = 2[W(H+L) + H x L)] = 2[16(13+33)+33 x 13] - Acp = 746 m2.

3.2.8.3 Absorptivity, α

α = 1- [0.0277 + 0.927 (x -1)] (x-1) ; where x refers to the pitch. Since pitch is 2, α = 0.879.

3.2.8.4 Sum of product of area and the absorptivities in the radiant zone

The equation for calculation is shown below: αAR = αAshield+ αAcp


Assuming the Ashield is negligible, then αAR = αAshield + αAcp
αAR = αAcp AR = Acp
Hence AR = 1584m2.

Production of Hydrogen via Syngas Route 3-15


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.2.8.5 Mean beam length

L = (2/3)(furnace volume)1/3 = 12.7m

3.2.8.6 Partial pressure of CO2 and H2O

The main combustion products are CO2 and H2O.


P = 0.288 – 0.229x + 0.0090x2; where x is the fraction of excess air taken to be 0.15.
Hence P = 0.256.

3.2.8.7 Product of partial pressure and mean beam length

PL = 0.256 x 12.7 = 3.24

3.2.8.8 Mean refractory tube wall temperature

Tt = 100 + 0.5 (T1 + T2)


From the SMR personnel: T1 = 539.4°C and T2 = 862.85°C.
Hence Tt = 783°C = 1384°F

3.2.8.9 Two main equations that will be used for iteration to find Tg (flue gas temp)

3.2.8.9.1 Radiant zone heat transfer

 Tg + 460  4  T + 460  4 
  + 7(Tg − Tt )
QR
= 1730   −  t
αAR F  1000   1000  

3.2.8.9.2 Radiant zone heat balance

QR Qn  Qa Q f Q L Q g 
= 1 + + − − 
αAR F αAR F  Qn Qn Qn Qn 
The unknowns in the equations also require approximation of Tg to be made.

Production of Hydrogen via Syngas Route 3-16


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

Qf
refers to the enthalpy of the fuel feed and is taken to be negligible as it is not preheated.
Qn
QR is related to Qn by the efficiency.
Qn = QR/efficiency where efficiency = 94% as computed earlier
Qa
refers to the enthalpy of the preheated air and will be taken from HYSYS simulation.
Qn

3.2.8.9.3 Enthalpy of the flue gas as a function of Tg (flue gas temp)

Qg   T  T 
= a + b − 0.1 − 0.1
Qn   1000  1000 
Z = fraction excess air
a= 0.22048-0.35027*z+0.92344*(z)^2; b=0.016086+0.29393*z-0.48139*(z^2)

3.2.8.9.4 Emissitivity of the gas Ф

Ф = a + b(PL) + c(PL)2 where PL was calculated earlier on


Z = (Tg+460)/1000
a= 0.47916-0.1984*z+0.022569*(z^2); b= 0.047029+0.0699*z-0.01528*(z^2)
c= -0.000803-0.00726*z+0.001597*(z^2)

3.2.8.9.5 Exchange factor F

F = a + b Ф + c Ф2 Z = Aw/αAR
a=0.00064+0.0591*z+0.00101*(z^2); b=1.0256+0.4908*z-0.058*(z^2)
c=-0.144-0.552*z+0.04*(z^2)

Production of Hydrogen via Syngas Route 3-17


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

After performing iteration using goal-seek tool in excel spreadsheet, the flue gas
temperature derived is 417°C. However the temperature as obtained from HYSYS is
565.6°C. However, since the heat exchanger network person-in-charge has decided to use
565.6°C for calculations in stream-matching, further computations and design for convection
section will make use of this value.

Since the temperature is low, a check is


carried out to ensure that the dew point of the
flue gas is not reached. The graph below shows
the dew point temperature of flue gas at different
temperatures.13.

Fig 3.2.8.9.5a14: Dew point of flue gases versus


fuel sulphur

Given that the excess air is 15%, and that there is 0wt% sulphur in fuel, the dew point
if about 130°F, which is lower than the flue, gas temperature computed (410°C). Hence the
flue gas temperature computed is reasonable.

3.2.9 Residence Time

Residence time = volume of each reformer tube / volumetric flow rate of reactant gas
= π x (D/2)2 / (mass flow per tube/ density)
= 1.286s

Production of Hydrogen via Syngas Route 3-18


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.3 CONVECTION SECTION

The convection section is used to preheat streams from other parts of the plant. This
helps to maximise the amount of energy that can be extracted from the furnace. Shield tubes
are omitted as convection tubes are not receiving direct heat from the flame from the
proposed design of the fired heaters. As discussed with the Heat Exchanger Network person-
in-charge, three process streams will have to be heated and the heating scheme will be as
shown below.

Steam will first be generated followed by heating up the SMR feed and finally
preheating the air fuel feed.

3.3.1 Convection design – Finned tubes

In the design of finned tubes, the following equation will be used.


Qc (Tg1 − TL1 ) − (Ts − TL 0 )
Ac = ; where LMTD =
U c (LMTCD ) [
ln (Tg1 − TL1 ) /(Ts − TL 0 ) ];
T L0 and TL1 = inlet and outlet temperature of process fluid (respectively)
Tg1 and Ts = temperature of incoming and outgoing flue gas (respectively)

Production of Hydrogen via Syngas Route 3-19


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

From the Heat Exchanger Person-in-charge, the following information is derived.

Process streams Heat duty KW LMTD Uc (W/m2K)


Steam 32090.7 87.5,360.7 10
Natural Gas 7307.5 61.4, 334.6 6.68
Air 4720.5 119.5,392.7 8.78

The total area is then calculated to be 8858.7 + 3268.6 + 1368.1 = 13495.4m2.


From the HEN person-in-charge, the desired outer diameter is 0.01905m = 0.75 in.
From the vendor of finned tubes (Vulcan Tubes), an appropriate fin tube is chosen.

The fin dimensions17 are shown below:

Number of fins per inches 7


Fin thickness (in.) 0.06
Fin height (in.) 0.625 = 0.015m
Surface area (sq ft per linear foot) 3.39

Total length of tubes needed = 145251 / 3.39 = 44015ft = 13338m

Section Total Length of each section (m)


Steam 8755
SMR feed 3126
Air 1352

Since the length of each tubes is very long, pressure drop will be high and hence the stream
has to be split into different tubes to prevent high pressure drop.
Section Number of tubes
steam 1250
SMR feed 446.47
Air 193
Number of tubes required = 13338 / 7 = 1905 tubes

Production of Hydrogen via Syngas Route 3-20


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

To ensure a mass flow of flue gas to be 1.7kg/s-m2, the


number of tubes is computed as:
Flow rate of flue gas is 86.88kg/s;
Cross section area of tubes = 86.88/1.7 = 51m2.
Width of cross section = 51/7 = 7.29m
Number of tubes along the cross section
= 7.29 / (2 x (0.01905+0.015=0.03405)) = 107 tubes

Hence the numbers of rows of tubes are 404 / 22 = 17.8 rows

Assuming the same pitch, height of convection section = 18 x 2 x 0.03405 =1.21m


Final dimension of the convection box is: 1.21m (Height) × 7m (Length) × 7.29m (Width)

3.3.2 Design parameters for convection tubes

Dimensions and tube material as provided by Heat Exchanger Network (HEN) counterpart:

Thickness (m) 0.002


Outer diameter (m) 0.01483
Tube nominal size15 Schedule 10
Tube material Carbon Steel

The minimal thickness to withstand the creep of carbon steel is found using the
equation as used for HK40 calculated above (for thickness of reformer tube minimum wall
d 
P i + FCA 
=  
min 2
thickness), t wall
S a E − 0.6 P

Given that the creep rupture strength of carbon steel is 54000 psi, the thickness is
0.00285in. Hence the minimum requirement is satisfied.

Production of Hydrogen via Syngas Route 3-21


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.3.3 Pressure drop in the tubes present in furnace

The typical pressure drop for crude unit heaters is between 150-250 psi. An additional
20-25 psi is added for fouled tubes. In order to satisfy this condition, the number of passes
and tube size has to be optimized.

Flow of the fluid within the furnace pipes is turbulent, via Reynolds number: Re = Di ρV µ .
Thus, a correlation developed by Haaland19 was used to determine the Fanning friction factor:
1/ [
f f = −3.6 log 10 (6.9 / Re ) + (e / 3.7 Di )
10 / 9
]

The following conditions must be satisfied to accurately determine the friction factor with
this correlation: (a) 10 8 ≥ Re ≥ 4 × 10 4 ; (b) 0.05 ≥ e / Di ≥ 0
Otherwise ff = 16/Re (for laminar flow)
Computation of the frictional head loss for a straight pipe is evaluated using the relation:
hL = 2 f f LV 2 / (2 gDi )

The pressure drop across the straight pipe is then given by: ∆Pp = ρhL

Presence of 180° bends within the 2 sections also contribute to the pressure drop
because the direction of flow changes. For each bend, a friction loss factor of K=1.6 is used
to compute the head loss. Subsequently, the pressure drop is obtained:
∆PB = ρhL = KV 2 / (2 g )

The total pressure drop in the tubes is evaluated by addition of the pressure drop
across straight pipes and the bends: ∆PT = ∆P1 + ∆P2

Production of Hydrogen via Syngas Route 3-22


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

The pressure drop for the following streams is computed. For the SMR stream,
pressure drop through bends is neglected as the tubes are straight.

Stream SMR tubing Steam in SMR feed in Preheated air


in radiation convection convection in convection
section section tubes tubes

Re 852 7934 7334 230.67


Fanning friction factor 0.0188 0.00202 0.00218 0.0694
(assuming smooth tube)
Friction head loss 0.103 0.142 346.6 154062

Pdrop through straight - 112 3982 180247


tube (psi)
Pdrop through bends - - - -
(psi)
Total Pdrop (psi) 0.109 112 3982 180247

It is noted that the pressure drop across the tube for preheating SMR feed and for
preheating air feed is much higher than the typical value. However, as this design is based on
the inner diameter as supplied by the heat exchanger network person-in-charge, this problem
will only be brought up for further mitigation on the best diameter for the convection tubes.
The pressure drop for SMR tubing is negligible, which is ideal for the steam methane
reforming reaction.

Production of Hydrogen via Syngas Route 3-23


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.4 STACK DESIGN

The stack is designed to direct the flue gas out of the furnace into the atmosphere as
well as to achieve a draft of required combustion air through the furnace. The stack height
must be sufficient to achieve this flow without imposing a positive pressure on any part of the
furnace chamber18. The usual practice is to maintain a small negative pressure in the furnace
to enable the introduction of air from the atmosphere. It also allows for the removal of
undesirable products from the furnace. The required stack height is dependent on the
temperature of the flue gas leaving the convection section and the difference in density of the
flue gas and the atmospheric air.

3.4.1 Stack diameter

An acceptable velocity for the flue gas velocity is found12 to be 7.6m/s. Assuming that
the stack is a uniform cylinder,
Diameter = [(volumetric flow rate of flue gas) / (π x flow rate)] ^ 0.5 = 4.96m

3.4.2 Pressure Drop across stack

3.4.2.1 Stack exit loss

The stack exit loss is computed as follows: ∆P1 = 0.176 KV g2 / (Ta + 273)

Velocity of flue gas = 11.5m/s ∆P1= 0.0783kPa

3.4.2.2 Frictional Loss in stacks and ducts

The flow in the stack is turbulent and hence the von Karman’s equation is used.
1/ f f = 4 log10 [Ds / e] + 2.28 ∆P2 = 2 f f HV g2 / ( Ds g )

Assume the roughness factor is 0.5, ff= 0.86. H is taken to be 4m as an initial guide.
∆P2= 0.0186 kPa

Production of Hydrogen via Syngas Route 3-24


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.4.2.3 Stack entrance loss

Stack entrance loss takes into account the full velocity head loss due to a change in
direction as the stack gas exits the furnace.
∆P3 = 0.176V g2 / (Tstack + 273) ∆P3= 5.5×10-5 kPa

3.4.2.4 Flue gas pressure drop through the convection section

Gunter Shaw’s correlation is used for pressure drop of a bank of helical bank tubes of
staggered arrangements.
0 .4 0.6
fG 2 L p  d ev   SL 
∆P4 =     ∆P4 = 1.11×10-5 kPa
( ρ g / ρ w )5.22 × 10 d evφ s  S T
10
  ST 

3.4.2.5 Pressure drop at the top of the radiant section

A vacuum of 2 mm H2O gauge just below the convection section is to be maintained


to prevent leakage of flue gas through the casing of the furnace. Hence ∆P5 = 0.0020kPa.

3.4.2.6 Pressure gain at the convection section

The stack effect at the convection section brings about a pressure gain in the furnace.
This gain is caused by the density difference between the hot flue gas and the ambient air
outside.

∆P6= 2.7 x 10-2 kPa ;


Total Pdrop across stack = ∆P1 + ∆P2 +∆P3 + ∆P4 +∆P5 +∆P6 = 0.0720kPa

Production of Hydrogen via Syngas Route 3-25


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.4.3 Stack Height

A stack height of 4m has been approximated


for calculation of pressure drop through the stack.
The stack height is calculated again to ensure that the
approximation is correct. According to the Code of
Practice on Pollution Control by National
Environment Agency (NEA), the stack height should
be at least 15m from the ground.

This is so that the hot stack gases are


discharged at a safe height with respect to the
surrounding equipment in the plant. In addition, the
flue gas may contain pollutants such as SOx, NOx and
particulates. Hence, the stack must be designed to
discharge these gases in a manner that avoids causing
a local pollution problem.

The equation used to calculate the stack height:

 
Pd = 0.35 H g Patm  1 − 1 
 aT T ga 

Pd = 0.0720kPa. H is found to be 10m. Hence the average height is taken to be 8m.

Production of Hydrogen via Syngas Route 3-26


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.5 MATERIALS FOR CONSTRUCTION OF FURNACE BODY & ADDITIONAL


AUXILIARIES

3.5.1 Refractory walls

The refractory walls are to be made of strong material that can withstand high
temperature. It also must resist abrasion and flue gas and most importantly, it should have a
high insulation to prevent heat loss to the surrounding.

In this design, silica brick (97-98% silica) with a thickness of 5-8 inches is selected to
line the furnace walls. It has the ability to retain its strength at high temperatures. A highly
porous fire clay insulating firebrick (1”) is placed between this lining & the metal casing.

The silicon carbide coating is light, low in thermal conductivity and sufficiently
resistant to temperature for the use on the hot side of the furnace wall. Thus, it permits thin
walls of low thermal conductivity and low heat content. The low heat content is particularly
valuable in saving fuel and time on heating time.

The properties of the silicon carbide and insulating wall are shown below.
Properties Silicon Carbide Insulating Brick
Thermal shock resistant Excellent Excellent
Hot strength/ Excellent/ Poor/
Deformation under hot loading/ Excellent/ Poor/
Permeability Very Low High
o
Fusion pt ( F) 4175 Varies
3
Bulk density lb/ft 160 30-75
Composition SiC 80-90% Varies

To further confirm that the refractory material chosen will be able to withstand high
temperature from the flames, Stefan-Boltzman equation will be used: q r = σT 4
Given that the radiant heat flux is about 25,000 BTU/h-ft2, which is 7.9 × 104 W/m2, T (wall
temperature) = 1086K = 1495F which is less that the fusion pt of silicon carbide and hence
this material is suitable for use.

Production of Hydrogen via Syngas Route 3-27


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.5.2 Stack Walls

Stainless steel will be used15 for construction of stack walls instead of insulating brick.
This reduces the cost and will exert less stress to lesser weight of the material. Stainless steel
melts at around 1370°C. Since the maximum temperature within the stack is approximately
565°C, stainless steel is suitable to form the stack wall.

However, it is important to note that since metal is involved, the temperature within
the stack should be kept above 150°C, which is above the dew point of water to prevent
condensation and thereby the formation of acid which will corrode the metal.

3.5.3 Additional auxiliaries

3.5.3.1 Air Preheaters

There are commercially available air preheaters to heat up the furnace air feed. One of
the commercially available air preheater is the Rekuluvo® Recuperative Air Preheater. Air is
preheated prior to burning in the furnace to ensure higher heat recovery. This

The good accessibility to heating surfaces allows easy maintenance. In addition, it is


corrosion resistant and does not have any mechanical moving parts that need additional
power supply.

Production of Hydrogen via Syngas Route 3-28


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.5.3.2 Forced Draft Fan

Forced draft has to be installed at the inlet of the furnace to draw air supply to the
furnace. This is because after being preheated by heat exchangers, the pressure of the air
supply drop by 3 psi for each heat exchanger. Having passed through 3 heat exchangers, the
pressure drop would be 9 psi in total.

The final pressure before entering the fired heater might be 14.5 – 9 = 5.5 psi, which
is very low. The forced draft will be used to increase the pressure of the air supply to 1atm
prior to feeding into the fired heater.

3.5.3.3 Induced Draft Fan

Induced draft fan is placed at the outlet of the furnace to draw the flue gas out of the
stack. A pressure of 2mmH2O less than atmospheric pressure is maintained. The proposed
force and induced draft fan are shown below.

Since both types of draft are used, the set-up is known as balanced draft. The fans
will be chosen in a way that the pressure is slightly below atmospheric pressure. This ensures
safe operation and reduces leakage of air into the furnace.

Production of Hydrogen via Syngas Route 3-29


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.6 COST ANALYSIS

3.6.1 Purchased Equipment Costs

Preliminary cost estimation was done to estimate the furnace and its auxiliary
equipment cost using the CAPCOST program developed by Turton.

3.6.1.1 Costing for Furnace

The bare module cost of reformer furnace before accounting for inflation is calculated
from Equation (3-1). Equation (3-2) gives the pressure factor (Fp) for the furnace. As carbon
steel is the base material used, the material factor, FM, is 2.1
.
(3-1)

for P < 10 barg (3-2)

(3-3)

where Ft (superheat correction factor for steam boilers) = 1 for heaters and furnaces
Identification number for HK40 alloy steel is 54, hence bare module factor FBM = 2.5

The various parameters that will be used for cost estimation:


Parameter Unit Value
A, Heat Duty KW 1.65 x 105
Pbarg barg 1
FM 2.5
FP 1
CBM= USD 1.545 x 1012

As the data for the equations were obtained during May to September 2002 when
Chemical Engineering Plant Cost Index (CEPCI) was 395.6, inflation should be accounted
for using the CEPCI of 595.1 in the last quarter of 2007 to USD 2.32 x 1012.

Production of Hydrogen via Syngas Route 3-30


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.6.1.2 Costing for Air Preheater

The bare module cost of the air preheater was approximated to that of a flat plate heat
exchanger because of the difficulty of getting the actual cost from vendors. Carbon steel was
chosen as the base material. Similarly, the bare module cost is calculated with equation 3-4.
C BM = C op (0.96 + 1.21FM Fp ) (3-4)

Parameter Unit Value


2
A, Area M 160
Pbarg barg 1
FM 1
FP 1

After taking inflation into account by using the CEPCI of 512 in the last quarter of
2006, the estimated cost of the air preheater is US$256,000.

3.6.1.3 Costing for Induced Draft Fan and Forced Draft Fan for Air Preheating System

The induced and forced draft fans selected are centrifugal fans, thus the bare module
cost can be approximated with that of the centrifugal radial fan. For both, carbon steel was
selected as the bare material since only flue gas and combustion air will be in contact with
them at relatively low temperatures.
C BM = C op FM Fp
(3-5)
The table below shows the Fans Bare Module cost parameters

Using the same CAPCOST Program, and after taking inflation into account, the
estimated cost of the induced draft fan is US$13,500 and forced draft fan is US$52,000.

Production of Hydrogen via Syngas Route 3-31


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.6.1.4 Burners

There are 3072 small premix burners used for this operation. Assuming each of the
premix burner cost USD 100, the total cost is USD 307200.

3.6.2 Utility Cost

Electricity (440V, 3-phase, 50Hz) – USD 100/MWh

Natural gas feed is not considered for furnace operation as the off gas from the PSA is
sufficient to supply enough heat energy required.

3.6.2.1 Electricity cost

The units of the furnace that runs on electricity are the induced and forced draft fans.
Hence, the electricity consumption will be based on the Horsepower rating of the individual
models that were selected according to the required capacity of volumetric gas flow rate.
Fan Horsepower Power (KW)
Induced Draft 25 19
Forced Draft 30 22

Given the power rating, the amount of electricity to operate both fans is US$14,300/year.

3.6.3 Total Annual cost

Assuming 15 years of operation:


Total annual cost = total bare module cost / 15 years + operating cost per year
Total annual cost = USD 1.55 x 105 million per year

Production of Hydrogen via Syngas Route 3-32


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.7 SUMMARY & CONCLUSION

In this project, a fired heater design for the steam methane reforming process has been
developed. The design methodology was presented. Design of the fired heater began with
consideration of the reaction heat energy requirement. The radiation section is then designed
with heuristics and maximum temperature specifications in mind.

After the completion of the radiation zone design, the convection design was explored
to increase the efficiency of the fired heater. The streams to be heated in the convection zone
were identified and the stream data and tube dimensions were obtained from the heat
exchanger person-in-charge. With the information available, the finned tube arrangements
were determined and the sizing of the convection section was obtained.

Both design process paid attention to heuristics and chances for optimisation.

Finally, stack design was carried out to meet specifications by governmental bodies.
Costing was then performed to determine the total annual cost of the fired heater constructed.

Production of Hydrogen via Syngas Route 3-33


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.8 SPECIFICATION OF FIRED-HEATER

Service: Steam Methane Reforming


Design Duty: 5.6 x 108 BTU/h Unit: Vacuum Unit heater
No. of heaters 1 Type: Box
Design Radiant Section Convection Section (Total)
Service SMR Preheating Streams
Heat absorption 561 108.6 15.9 24.7
(mmBTU/h)
Fluid SMR Process Superheated Air SMR feed
Fluid steam
Allowable pressure 150-200
drop (psi)
Allowable average heat 25000
flux (BTU/h-ft2)
Fouling factor 0
Residence time N/A
Inlet Conditions
Temperature (°C) 539.4 253.3 25 25
Pressure (kPa) 2679 4200 100 4000

Liquid flow (kg/h) N/A 1.743 x 105 N/A N/A


Vapour flow (kg/h) 1.835 x 105 N/A 2.997 x 105 4.3 x 104
Liquid density (kg/m3) N/A 790.7 N/A N/A
Vapour density(kg/m3) 7.059 N/A 1.167 28.99
Viscosity(cST) 3.497 0.1336 16.12 0.4180
Specific heats 46.29 99.98 29.24 40.72
(KJ/KJmole-C)
Thermal conductivity 0.08 0.6121 0.02586 0.0369
(W/m-K)
Design Radiant Section Convection Section (Total)
Outlet
Temperature (°C) 851.9 254.3 80.30 250
Pressure (kPa) 2630 4179 79.32 3979
Liquid flow (kg/h) N/A N/A N/A N/A
Vapour flow (kg/h) 1.835 x 105 1.743 x 105 2.997 x 105 4.3 x 105
Liquid density (kg/m3) N/A N/A N/A N/A
Vapour density(kg/m3) 3.55 20.27 0.7804 15.10
Viscosity(cST) 8.662 0.8705 27.33 1.192
Specific heats 38.47 43.58 29.57 49.05
(KJ/KJmole-C)
Thermal conductivity 0.2003 0.05 0.02972 0.07
(W/m-K)

Production of Hydrogen via Syngas Route 3-34


CN 4120: Design II
Team 32: Ng Su Peng (U046929L) Furnace Unit Design Report

3.9 REFERENCES

1. Furnace/ Fired Heater Design and Control Lecture notes


2. Robin Smith. (2005). Chemical Process Design and Integration. John Wiley & Sons.
3. W. L. Nelson. (1985). Petroleum Refinery Engineering, Auckland. McGraw-Hill
4. V. Ganapathy. (1982). Applied heat transfer. PennWell.
5. Role of Alloying Elements. Retrieved from World Wide Web on 16 Mar 2008:
http://www.valve-world.net/pdf/11022.pdf
6. Retrieved from World Wide Web on 30 Mar 2008:
http://www.fitness4service.com/publications/pdf_downloads/Jaske-Shannon%20Paper.PDF
7. Inspection and Remaining Life Evaluation of Process Plant Equipment. Retrieved from
World Wide Web on 16 Mar 2008: http://www.kubotametal.com/alloys/heat_resistant/HK-
40.pdf
8. Dilton, C.P. (1992). Materials selection for the chemical process industries.
9. Role of Alloying Elements. Retrieved from World Wide Web on 16 Mar 2008:
http://www.valve-world.net/pdf/11022.pdf
10. Rostrup-Nielsen, J. (1993). Steam Reforming Opportunities and Limits of the Technology,
Catalysis Today, Vol. 18, P305-324.
11. James R. Cooper, W. Roy Penney, James R. Fair. (2005). Chemical Process Equipment,
Second Edition: Selection and Design. Elsevier.
12. R.K. Sinnott, Coulson & Richardson's chemical engineering - Volume 6: Chemical
engineering design, Elsevier Butterworth-Heinemann (2005)
13. D.S.J. Jones. (1996). Elements of Chemical Process Engineering. John Wiley & Sons.
14. Melting Point of Iron – Jefferson Lab. Retrieved from World Wide Web on 20 Mar 2008:
http://72.14.235.104/search?q=cache:3kYX9gKVDVEJ:education.jlab.org/qa/meltingpoint_0
1.html+melting+point+of+steel&hl=en&ct=clnk&cd=1&gl=sg
15. James R. Welty, Charles E. Wicks, Robert E. Wilson & Geogory Rorrer. (2001).
Fundamentals of Momentum, Heat, and Mass Transfer – 4th Edition. John Wiley & Sons, Inc.
16. S. Singh, S Goyal. (2002). Fired Heaters in Chemical Process Industries CPECNews:P2-6
17. Retrieved from World Wide Web on 30 Mar 2008: http://www.vulcanfinnedtubes.com/
18. R.K. Sinnott. (2005). Coulson & Richardson's Chemical Engineering - Vol 6: Chemical
engineering design. Elsevier Butterworth-Heinemann.
19. S. E. Haaland. (1983). Trans. ASME, JFE: Vol. 105, P89

Production of Hydrogen via Syngas Route 3-35


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Chapter 4 : HIGH TEMPERATURE SHIFT REACTOR


4.1 INTRODUCTION

Hydrogen is an extremely important compound required in our lives. It is used to


provide food, fuel and chemical resources for us. The largest processes using hydrogen are
ammonia synthesis, methanol synthesis, and hydrogenation. Without it, it would cause us to
live very differently in the world today. The production of hydrogen can be carried out using
steam reforming of any hydrocarbon source such as coal, methane, petroleum naphtha or
biomass. Methane is usually used due to its cheaper costs than the other hydrocarbon sources.

4.1.1 Water gas shift

During the steam reforming stage, side reactions happening in the steam reformer
would cause carbon monoxide to be formed, and this limits the production of hydrogen. Thus,
water gas shift reaction was developed to obtain more hydrogen from carbon monoxide.
This is the water gas shift reaction:
CO + H 2 O ⇔ CO2 + H 2
which involves the reaction of carbon monoxide and water in the presence of a suitable
catalyst to form carbon dioxide and hydrogen.

There are three alternatives for carrying out the reduction of CO. [1]
1. Remove part of CO with iron catalyst in one bed. Then absorb CO2 and go to a second
bed of the same catalyst with a more favourable equilibrium since the product CO2 is
absent.
2. Conduct the entire reaction in a single bed on copper-zinc catalyst.
3. Remove part of the CO in a bed with iron catalyst and complete the removal in a
second bed of the more expensive copper-zinc catalyst.

The second and third alternatives are more attractive as the additional absorption equipment
in the first alternative creates added maintenance problems, particularly due to the corrosive
character of monoethanolamine, which is the usual absorbent used.

Production of Hydrogen via Syngas Route 4-1


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

For the purpose of this design, I have decided to use the third alternative. This is because the
second alternative would be much more expensive. The cost of copper-zinc catalyst is 3 times
the cost of iron catalyst. Therefore, it is justified to use alternative 3, to achieve the required
CO reduction.

4.1.2 High temperature shift

CO + H 2 O ⇔ CO2 + H 2 ∆H rxn = −44.447 kJ / mol

As seen from the enthalpy of the water gas shift reaction, it is an exothermic reaction.
Thermodynamically, the conversion of the reaction is favored at low temperature. The lower
the temperature is, the higher the conversion will be. However, at low temperatures, the rate
of reaction is slow. Though conversion is high, it might take a very long time for it to reach
that conversion equilibrium. Therefore, to ensure a high rate of reaction and a high overall
conversion, it is necessary to use a High Temperature Shift (HTS) followed by a Low
Temperature Shift (LTS). This mechanism is needed so that in the HTS reactor, the reaction
occurs at a reasonably high rate. Then the reaction is completed in the LTS, which would
ensure a reasonable overall conversion.

The higher temperature in the HTS reactor also allows recovery of the heat of reaction at a
sufficient temperature level to generate high pressure steam.
The HTS is usually conducted at a range of 315oC-480 oC. [1]

Production of Hydrogen via Syngas Route 4-2


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.2 PROBLEM DESCRIPTION

After Steam Methane Reforming (SMR), the products would be thrown into the HTS reactor.
The objective of the HTS reactor is to reduce carbon monoxide composition to 3% (dry basis).
This was justified by literature data. [1] After which, the products would be thrown into the
LTS reactor for further conversion so that the exit carbon monoxide composition would be
0.7% (dry basis).

Feed specification
The relevant data of the outlet stream from SMR are as follows:

Table 4.2.1: SMR outlet stream data


Flow rate (kmol/hr) 14470
Pressure (kPa) 2610
Temperature (K) 1125

Table 4.2.2: SMR outlet stream composition


Component Mol fraction Molar flow (kmol/hr)
CH4 0.03493 505.4
H2O 0.34518 4994.8
CO 0.08737 1264.3
CO2 0.05451 788.8
H2 0.47513 6875.2
N2 0.00072 10.4
C2H6 0.00216 31.2

Steam-to-CO Ratio
According to literature, steam to carbon monoxide ratio must surely be more than 4:1.[1] The
optimum amount of steam to be used is based on economic considerations, such as the cost of
steam. Furthermore, using more steam requires equipment with a larger diameter due to a
greater flow rate.

Production of Hydrogen via Syngas Route 4-3


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

From the above table, the steam to carbon monoxide molar ratio is 4:1. However, it was still
unable to achieve a reduction of CO to 3% (dry basis) at this steam ratio. Therefore, steam
was added to make the steam to carbon monoxide molar ratio 5:1. This was justified by
literature data, as they also used a steam to carbon monoxide ratio of 5:1. [1] Doing this
would reduce the amount of catalyst needed, as well as make it possible to achieve a
reduction of CO to 3% (dry basis).

Amount of steam added = [(1264.3 × 5) − 4994.8] kmol/hr


= 1326.6 kmol/hr

After adding 1326.6kmol/hr of steam to make the steam to carbon monoxide molar ratio (5:1),
also cooling the inlet stream down to 627 K, and assuming a pressure drop of 20.88kPa
across the heat exchanger, the HTS inlet stream data are as follows:

Table 4.2.3: HTS inlet stream data


Flow rate (kmol/hr) 15796.6
Pressure (kPa) 2589.12
Temperature (K) 627

Table 4.2.4: HTS inlet stream composition


Component Mol fraction % composition Molar flow
(dry basis) (kmol/hr)
CH4 0.03200 5.33 505.4
H2O 0.40017 - 6321.4
CO 0.08004 13.34 1264.3
CO2 0.04993 8.32 788.8
H2 0.43523 72.56 6875.2
N2 0.00066 0.11 10.4
C2H6 0.00198 0.33 31.2

Production of Hydrogen via Syngas Route 4-4


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Product specification

Therefore, the problem is defined to reducing carbon monoxide from 13.34% (dry basis) to
3% (dry basis).

This is the table of the compositions of the HTS outlet stream after the single fixed bed
catalytic reactor was designed:

Table. 4.2.5 HTS outlet stream composition


Component Mol fraction % composition Molar flow
(dry basis) (kmol/hr)
CH4 0.03200 4.85 505.4
H2O 0.33994 - 5369.9
CO 0.01980 3.00 312.8
CO2 0.11017 16.69 1740.3
H2 0.49546 75.06 7826.6
N2 0.00066 0.10 10.4
C2H6 0.00198 0.30 31.2

Conversion of CO in designed HTS reactor = (1- 0.01980/0.08004) x 100%


= 75.27%

Production of Hydrogen via Syngas Route 4-5


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.3 REACTION THERMODYNAMICS

4.3.1 Criteria for Chemical Reaction Equilibrium

The fundamental property relation for single-phase systems, provides an expression for the
total differential of the Gibbs energy:
` a ` a ` a
d nG = nV dP @ nS dT + Σ ui dni (4.3.1.1)
i

If changes in the mole numbers ni occur as the result of a single chemical reaction in a closed
system, then by substituting dni = v i dε , equation (2.3.1.1) gives:
` a ` a ` a
d nG = nV dP @ nS dT + Σ v i ui dε (4.3.1.2)
i

Because nG is a state function, the right side of this equation is an exact differential
expression; thus,
` a
F∂fffffffffffffffffffff
nG G F ∂G t
ffffffffffff G
Σ v i ui = =
i ∂ε ∂ε
T,P T,P

Thus the quantity Σ v i ui represents the rate of change of total Gibbs energy of the system
i

with respect to the reaction coordinate at constant T and P. This quantity is zero at the
equilibrium state. A criterion of chemical-reaction equilibrium is therefore:
Σ v i ui = 0 (4.3.1.3)
i

The definition of the fugacity of a species in solution is as such:


` a ^
µ i = Γ i T + RTln f i
In addition, the following equation may be written for pure species i in its standard state at
the same temperature:
o ` a o
G i = Γ i T + RTln f i
The difference between these two equations is:
^

o fi
ffffffff
µ i @G = RTln i o (4.3.1.4)
fi
Combining equation (4.3.1.3) with equation (4.3.1.4) gives for the equilibrium state of a
H I
f g vi
J o ^ ) o K
chemical reaction: Σ v i G i + RTln f i fi =0
i

Production of Hydrogen via Syngas Route 4-6


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report
f g vi
^ ) o
Σ v i G + RTΣ ln f i f
o
or i i =0
i i

f g vi o
^ ) o @Σ vi G i
fffffffffffffffffffffffffff
or Π fi fi = i
i RT
where Π signifies the product over all species i. In exponential form, this equation becomes:
i

f g vi
^ ) o
Π fi fi =K
i

4.3.2 Effects of Pressure on Reaction Equilibrium

The equilibrium state of a chemical reaction is given as:


f g vi
^ ) o
Π fi f i =K (4.3.2.1)
i

Where Π represents the product over all species i, f is the fugacity of species i in solution,
o
f i is the fugacity of species i at standard state, and the equilibrium constant K is a function
of temperature only and is defined by:
f og
@∆G
K = exp ffffffffffffffffffff (4.3.2.1a)
RT

The standard state for a gas is the ideal-gas state of the pure gas at the standard state pressure
Po of 1 bar. Because the fugacity of an ideal gas is equal to its pressure, fio = Po for each
^ ) o ^ ) o
species i. Thus for gas-phase reactions fi fi = fi P , and equation

(4.3.2.1) becomes:
h ^ i vi
fi
Πj ffffffff
o
k =K (4.3.2.2)
i P

Equation (4.3.2.2) relates K to fugacities of the reacting species as they exist in the real
equilibrium mixture and these fugacities reflect the non-idealities of the equilibrium mixture.
The fugacity is related to the fugacity coefficient by:
^
f i = Φ^ i y i P

Production of Hydrogen via Syngas Route 4-7


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Substituting this equation into (4.3.2.2) yields an equation which relates the pressure to the
composition:
d e vi f g @v
^ P
ffffffff
Π yi Φi = o K (4.3.2.3)
i P

Where, v a P v i . Assuming that the equilibrium mixture is an ideal solution, then each Φ^i
becomes Φ i . Thus, equation (4.3.2.3) becomes:
b c vi f g @v
P
ffffffff
Π yi Φi = o K (4.3.2.4)
i P
Each Φ i for a pure species can be calculated from a generalized correlation once the
equilibrium temperature and pressure is specified. For low pressures or high temperatures, the
equilibrium mixture behaves as an ideal gas where Φ^i = 1. Thus, assuming that the
equilibrium mixture is an ideal gas, equation (4.3.2.4) reduces to:
f g @v
` av i P
ffffffff
Π yi = o K (4.3.2.5)
i P
In the WGS shift reaction, the stoichiometric coefficients of the reactants and products are all
` a
1 which means that v = P v i = 1 + 1 @1 @1 = 0 . Therefore, equation (4.3.2.5) reduces to:
` av i
Π yi =K (4.3.2.6)
i

From equation (4.3.2.6), it can thus be seen that the equilibrium constant of the WGS reaction,
K is independent of pressure. Thus, the pressure conditions within the HTS reactor will not
affect the equilibrium of the reaction.

4.3.3 Effects of Temperature on Reaction Equilibrium

From the first law of thermodynamics for a closed system of n moles, is as such for the
special case of a reversible process:
` a
d nU = dQ + dW (4.3.3.1)

` a ` a
As applied to this process, dW = @Pd nV and dQ = Td nS . Combining these three
equations gives:
` a ` a ` a
d nU = Td nS @Pd nV (4.3.3.2)

Production of Hydrogen via Syngas Route 4-8


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

The enthalpy and the Gibbs energy are defined as:


H a U + PV (4.3.3.3)
G a H @TS (4.3.3.4)

Upon multiplication by n, equation (4.3.3.3) may be differentiated to give:


` a ` a ` a ` a
d nH = d nU + Pd nV + Vd nP (4.3.3.5)
Substituting equation (4.3.3.2) into (4.3.3.5),
` a ` a ` a
d nH = Td nS + nV dP (4.3.3.6)
In the same way, equation (4.3.3.4) may be multiplied by n and differentiated to give:
` a ` a ` a ` a
d nG = d nH @Td nS @Sd nT (4.3.3.7)
Equation (4.3.3.6) and equation (4.3.3.7) combine to yield:
` a ` a ` a
d nG = nV dP @ nS dT (4.3.3.8)
In the application of equation (4.3.3.8) to a one mole of homogeneous fluid of constant
composition, equation (4.3.3.8) simplifies to:
dG = VdP @SdT (4.3.3.9)
An alternative form of equation (4.3.3.9) which is a fundamental property relation that
follows from the mathematical identity is:
f g
G 1 G
d ffffffffff a ffffffffffdG @ fffffffffffff
2
dT (4.3.3.10)
RT RT RT
Substituting equations (4.3.3.9) and (4.3.3.4) into (4.3.3.10):
f g
G V
ffffffffff H
d a ffffffffffdP @ fffffffffffff
2
dT (4.3.3.11)
RT RT RT
All terms in this equation are dimensionless. When applied in restricted forms,
H b cI
∂ G+ RT
H J ffffffffffffffffffffffffffffffK
fffffffffffff
@ 2 = (4.3.3.12)
RT ∂T P

The relation between the standard heat of reaction and the standard Gibbs energy change of
reaction may be developed from equation (4.3.3.12) written for each species i in its standard
state:
h b ci
o *
o
G RT
2j dffffffffffffffffffffffffffffffffffk
i
H i = @RT (4.3.3.13)
dT

Production of Hydrogen via Syngas Route 4-9


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

By multiplying both sides with ν i and summation over all species yields:
h b ci
o

o
d P vi Gi * RT
2j ffffffffffffffffffffffffffffffffffffffffffffffffffk
P v i H = @RT (4.3.3.14)
dT
o o o o
By definition, ∆G a P v i G i and ∆H a P v i H i . Thus equation (4.3.3.14) can be
i i

expressed as:
h b ci
∆G * RT
o
o 2j dfffffffffffffffffffffffffffffffffffffk
∆H = @RT (4.3.3.15)
dT
Substituting equation (4.3.2.1a), equation (4.3.3.15) becomes:
o
dln K ∆H
ffffffffffffffffff ffffffffffffff
= 2
(4.3.3.16)
dT RT

Equation (4.3.3.16) gives the effect of temperature on the equilibrium constant, and hence on
o
the equilibrium conversion. If ∆H is negative, i.e. the reaction is exothermic, the equilibrium
constant decreases as the temperature increases. Conversely, K increases with T for an
endothermic reaction. Since the water-gas shift reaction is slightly exothermic with ∆H = -
41.1kJmol-1, thus the equilibrium constant increases with decreasing temperature. Thus, it is
desirable to operate at the lowest possible reactor inlet temperature to obtain maximum
removal of carbon monoxide.

Production of Hydrogen via Syngas Route 4-10


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.4 REACTION KINETICS

The overall reaction is CO + H 2 O ⇔ CO2 + H 2


Using literature data [1], we have chosen Chromia-promoted iron oxide as our catalyst. This
catalyst has been used for many years for the shift reaction.

Rate Equation

The rate equation for this catalyst is shown below, and is assumed to represent midlife
activity:

ψk ( y CO y H O − y CO y H / K )
(−rCO ) = 2 2 2

379 ρ b

Where,
4900
k = rate constant = exp(15.95 − )
T
4578
K = equilibrium constant = exp(−4.33 + )
T
(-rCO) = rate, lb moles CO converted / (lb catalyst) (hr)
T = temperature, K
yj = mole fraction of component indicated
ρb = catalyst bulk density, lb/cu ft
ψ = 4.0 for P > 20.0 atm

The manufacturer has subjected the rate equation to many tests, as well as observations on
full-scale plants. The rate constants are expressed on the basis of a reasonable “lined-out”
activity that the catalyst would maintain for a considerable time, if operating errors which
cause deactivation do not happen. The ψ term is the product of the total pressure (atm) and
ratio of the first-order constant at pressure P to that at atmospheric pressure and is a function
of pressure and Thiele modulus. Thus, it is considered that the effectiveness factor of the
catalyst has already been taken into account in the ψ term.

Production of Hydrogen via Syngas Route 4-11


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.5 CATALYST

As mentioned, the catalyst used is chromia-promoted iron oxide. [1] The specifications of the
catalyst are as follow:

Table 4.5.1
Maximum operating temperature (oF) 890
Tablet size (inch) 0.25 x 0.25
Bulk density (lb/cu ft) 70
Particle density (lb/cu ft) 126
Catalyst poisons Inorganic salts, boron, oils, or phosphorous
compounds, liquid H2O is a temporary poison.
Sulfur compounds in an amount greater than
50ppm
Catalyst life 3 years and above, depends on care in startup
and operation (Use times up to 15 years have
been reported)

Production of Hydrogen via Syngas Route 4-12


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.6 REACTOR

An adiabatic single fixed bed catalytic reactor is used for the HTS reactor.

4.6.1 Type of reactor

The reason why the reactor was chosen as a single bed was because the heat of reaction for
CO + H 2 O ⇔ CO2 + H 2 was not that high. Therefore, temperatures in the reactor would not
rise by too much. A single bed would suffice to convert CO to its desired composition
without raising temperature too high such that conversion would be affected.

An adiabatic reactor was chosen because it is cheap and easy to maintain. It is not only the
lowest cost and simplest type of reactor, but its performance can be predicted reliably for
single phase reactions.

This is also justified by literature data as shown in the case study, where the author also used
an adiabatic single fixed bed catalytic reactor.

4.6.2 Reactor design

Vessel Design

Vessel costs are an important element in reactor design decisions. In the U.S.A. the American
Society of Mechanical Engineers has established a code for the design and fabrication of
pressure vessels. Similar organizations in Europe also have established codes. All such codes
give the minimum standards. Normally vessels as important as reactors are designed to
comply not only with a code but also with supplement specifications considered important for
a particular service. These can include special impact test requirements to assure against
brittle fracture, heat-treating specifications for steel in severe service such as high hydrogen
partial pressures. Below is a picture of the design of the vessel.

Production of Hydrogen via Syngas Route 4-13


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Fig. 4.6.2.1 Design of vessel

Corrosion Allowance

Although practices vary, on the average a material is selected that will not corrode more than
0.010 to 0.015 in. /yr. For a vessel of life 10 years, this approximates a corrosion allowance
of 1/8 in. Because of the many variables and unknowns associated with corrosion, a
minimum allowance of 1/8 in is specified for carbon steel and low alloy steel even if no
corrosion or erosion problems exist. For higher alloys, such as stainless steel, a lower
minimum of 1/32 in is often used.

Production of Hydrogen via Syngas Route 4-14


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Material Selection

In the case of hydrogen services which cause pitting, corrosion allowance may not be that
useful. Hydrogen destroys metal strength by producing cracks or blisters, but the thickness of
the metal is not reduced. At low temperature atomic hydrogen produce by thermal or catalytic
dissociation diffuses into the metal along imperfections, ultimately recombining to form
molecular hydrogen. The hydrogen pressure can increase to a point where it causes internal
and surface blistering. [4] At high temperatures, hydrogen diffuses even more rapidly and
forms methane by reacting with the carbon content of the steels. The larger methane molecule
builds up pressure that produces high internal pressure and ultimately cracks [5]. Neither of
these processes reduces the metal thickness. Thus one selects for high temperature service a
metal that will not be subjected to attack, containing a carbide stabilizing element such as
molydenum.

Thus the material ASTM A 387 Grade 22, Class 1 (2 ¼ Cr-1 Mo) was chosen for its
resistance to hydrogen attack.

Production of Hydrogen via Syngas Route 4-15


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.7 METHODOLOGY AND CALCULATIONS

4.7.1 Weight of catalyst

Methodology

The following equations were used in the calculations for weight of catalyst used
Mass balance equation:
∆W (−rCO ) = (−∆FCO ) (Eq. 4.7.1.1)
Heat balance equation:
∑ F j c p , j (T j +1 − T j ) = (− rCO )( −∆H CO ) T ∆W (Eq. 4.7.1.2)

= (−∆FCO )(− ∆H CO )
The heat capacities of gases were taken from literature text. [2]

Based on these equations and the rate equation, a MATLAB program was written based on
the following algorithm to find the mass of catalyst needed.
Algorithm
1. Input the inlet temperature of HTS in K.
2. Assume ∆W of 200lbs
3. Calculate (-rCO) at inlet conditions to increment, i.
4. Calculate (-rCO)avg = (-rCO)i + [(-rCO)i – (-rCO)i-1]/2 (skip for i=0).
5. Calculate new flow rates: Fi+1 = Fi ± (-rCO)∆W
6. 4. Calculate cp and (-∆HCO) @ Ti
7. Calculate ∆T from Eq. 4.7.1.2.
8. Ti+1 = Ti + ∆T
9. yi+1 = Fi+1/(FT)i
10. Mole fraction CO in dry gas = [yCO/(1-yH2O)]i+1
11. If mole fraction CO in dry gas is more than 3%, go back to step 1.
12. If mole fraction CO in dry gas is 3%, mass of catalyst is found as number of
increments multiplied by 200lbs.

The MATLAB program can be found in Appendix 4.12.1.

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CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Calculations

The temperature of inlet stream to the HTS reactor was varied to get the corresponding mass
of catalyst required to reduce CO to 3% (dry basis). This was done to optimize the mass of
catalyst used with its optimum inlet temperature of the inlet stream. Then, a graph was
plotted to show the relationship between mass of catalyst and inlet temperature.

Fig. 4.7.1.1 Graph of mass of catalyst against inlet temperature

From the graph, the minimum mass of catalyst needed was 121909 kg.
However, 5% more catalyst was added to allow for any degrading of catalyst.
Therefore mass of catalyst used = 1.05×121909kg = 128000kg

This occurred at the inlet temperature of 627 K. Thus, for the HTS reactor, the inlet stream
was fixed at 627 K.

Production of Hydrogen via Syngas Route 4-17


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

A temperature profile graph was also plotted in the figure below. The temperature range was
from the inlet stream of 627 K to that of the outlet stream was which calculated to be 693.2 K.

Fig. 4.7.1.2 Temperature profile graph

Production of Hydrogen via Syngas Route 4-18


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

A conversion profile graph was also plotted as shown below. The inlet CO was at 13.34% dry
basis and the outlet CO was 3% dry basis.

Fig. 4.7.1.3 Conversion profile graph

4.7.2 Pressure drop

Pressure Drop, though negligible in some reactors, can be a major concern in others. It is an
important variable in the rate equations for gaseous reactions. Since compressors and
compressor operating costs often dominate the economic structure of a reactor system,
pressure drop is not only important but must be predicted with good accuracy.

The resulting force must not exceed the crushing strength of the particles. In homogeneous
clean beds, one would expect the maximum stress to occur at the bottom of the bed, where
the weight of the catalyst combines with the stress created by the ∆P across the bed. In down
flow, this force created by the ∆P is transmitted by the contacting solids to the bottom of the
bed. Some catalysts are quite fragile and this issue demands close attention with sufficient
safety factor applied.

Production of Hydrogen via Syngas Route 4-19


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Mass velocities through the bed must be high enough to minimize inter-phase gradients and
assure good distribution. Incremental increases in ∆P, however, should not cause pumping or
compressing costs to exceed savings realized from improved reactor performance. In many
packed bed systems, the maximum economical ∆P is in the range of 3-15 % of the total
pressure.

In gaseous systems, higher pressure drop and thus higher velocity, also means smaller
diameter reactors, which can be important in reducing costs of high pressure reactors; but this
advantage can be offset by higher energy costs. The given fraction of plant pressure drop
allotted to drop across the bed is directly proportional to the fraction of power consumed,
which is essentially a function of energy costs and independent of total pressure. Thus
economic allowable ∆P will be a fixed fraction of total pressure and can vary from a few
inches of water for reactors operating near atmospheric pressure to several atmospheres for
reactors operating at higher pressure.

A unique value of particle density does not even exist for a given catalyst. Generally, smaller
sizes will have higher particle densities than larger sizes, which can be rationalized by
considering the limit of a catalyst approaching the size of an average pore. Dense packing in
a full-size bed is preferred for uniform flow distribution and is obtained by raking or
spreading the catalyst between each load. Although a rapidly dumped bed will result in looser
arrangement and lower pressure drop, it is more likely to cause channelling.

Although small catalyst particles have higher effectiveness factors, it is not wise to specify
sizes below 1/8 in. unless some means is provided for removing fines, dirt and scale from the
feed stream. The greatest care should be exercised in packing a bed to eliminate fines and dirt
and the reactor should be protected by suitable filters whenever plugging by scale or polymer
formation in upstream equipment is anticipated. These materials can be carried to the reactor
and deposited on the top part of the bed and limit the throughput drastically. Plugging of a
catalyst bed is a serious problem that can ultimately lead to shutdown and dumping of the bed
as pressure drop becomes excessive. Prior to this event, serious malfunction of the reacting
fluid can occur, resulting in poor yields and reduced production. The ability to predict clean-
bed ∆P is often foreshadowed by our inability to predict the rate and character of plugging
that may occur.

Production of Hydrogen via Syngas Route 4-20


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Methodology

For this HTS reactor, the inlet pressure is 2610kPa. Since maximum economical pressure
drop is in the range of 3-15% of the total pressure. [3] Taking pressure drop to be 4% of total
pressure.
∆P = 0.04×2610 kPa
= 104.4 kPa
≈ 1 bar
Therefore, a pressure drop of 1 bar is to be obtained.
These are the equations required to find the pressure drop and aspect ratio.
DpG
N Re = ,
µ
Where NRe = Reynolds’ number
6d c
Dp = = 0.25
dc
4+2
hc
µ = Average of inlet and outlet viscosity
1− ε
f k = 1.75 + 150 ,
N Re
Where fk = friction factor
ε = voidage
fkG2 1 − ε 
∆P =  3 L ,
Dp ρ f gc  ε 
Where G = mass flux
= mass flowrate per cross sectional area
ρ f = density of feed
L = length of reactor

Production of Hydrogen via Syngas Route 4-21


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

To find the aspect ratio of the reactor which corresponds to a pressure drop of 1 bar, the
following algorithm was used.

1. The volume of the total catalyst was calculated based on mass of catalyst used and
density. This volume is multiplied by 1.2 to give an extra 20% volume for the
allowance of inert support as well as poor packing of catalyst.
2. Calculate average µ (viscosity) based on inlet and outlet.
3. Assume a value of L

V 
4. Calculate the corresponding value of diameter, D = 2  
 πL 
5. Calculate aspect ratio, AR=L/D
6. Calculate G
7. Calculate ε
8. Calculate N Re
9. Calculate f k
10. Calculate ∆P
11. Go back to step 3 and assume another value of L to get corresponding ∆P .
12. Plot graph of ∆P against AR.
13. Identify the AR where ∆P =1 bar

The MATLAB program can be found in Appendix 4.12.2.

Production of Hydrogen via Syngas Route 4-22


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Calculations
The pressure drop against aspect ratio figure is plotted as shown below:

Fig. 4.7.2.1 Graph of pressure drop against Aspect ratio

Therefore, a pressure drop of 1 bar corresponds to an Aspect ratio of 3.497.


L
Solving simultaneous equations = 3.497 -------------- (1)
D
V= Mass of catalyst/ bulk density
V= 113.92m3
2
D
π  L = 113.92 --------(2)
2

L, length of reactor = 12.11m


D, diameter of reactor = 3.46m

Production of Hydrogen via Syngas Route 4-23


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.7.3 Thickness of vessel

With an internal pressure of 2610 kPa and diameter of 3.46m=11.35ft,

Design Pressure: 2610 x 1.2 x 0.145 = 454.2 psi, taking into account an allowance of 20% for
increased operating pressure
Design Temperature: 890 0F (maximum catalyst use temperature)
S = 13100 psi
E, the joint efficiency = 1.0, for double butt welded and fully radio-graphed welds
Minimum Corrosion allowance = 1/8 in.

PR 454.2 × 5.68 × 12
t= = = 2.413 in
SE − 0.6 P (13100 × 1.0) − (0.6 × 454.2)

t actual = 2.413 + 0.125 = 2.538 in

The MATLAB program used to solve this can be found in Appendix 4.12.3.

4.7.4 Reactor size and cost

Catalyst cost

Mass of catalyst = 128000 kg


Cost of catalyst = US$20/cu ft in 1977
Particle density of catalyst = 126 lb/cu ft
Volume of catalyst = 2234.9 cu ft
CEPCI in 1977 = 204.1
CEPCI in 2006 = 499.6
Cost of catalytic bed = 2234.9 x $20 x 499.6/204.1
= US$109,414

Production of Hydrogen via Syngas Route 4-24


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Vessel Costs

From the literature data [1], the vessel cost can be estimated as follows:

Using 2:1 elliptical heads of same thickness


Material Density: ( ρ = 490 lb/ cu ft)
2.538
Shell, π × 11.35 × ( ) × 39.72 × 490 = 146,778 lb
12
Heads
π 2.538 2 2.538
490 × × [(1.23 × 11.35) + ] × × 2 = 32,696 lb
4 12 12
Total Weight = 146,778 + 32,696 = 179,474 lb

For this size and type vessel, a fabricated cost of 73 cents/lb without nozzles was suggested
as an estimating figure (1971 cost) by a fabricator.

CEPCI in 1971 = 132.3


CEPCI in 2006 = 499.6
499.6
Cost of vessel= 179474 × 0.73 × = US $494,750
132.3

Production of Hydrogen via Syngas Route 4-25


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.8 HEAT EXCHANGER

With a conversion of 75.27% CO, a conversion reactor is simulated in Hysys. This is the
figure that is extracted from Hysys to get the duty needed to cool down the HTS outlet before
it goes into the LTS inlet. The LTS inlet is to be cooled to 493.1K.

Fig. 4.8.1 Hysys diagram of HTS reactor

The duty needed to cool the HTS outlet stream from 692 K to 493.1K is 1.099e+008 kJ/hr
according to Hysys. However, the actual HTS outlet temperature as calculated from
MATLAB is 693.2K. This is quite close to the calculated value from Hysys. The actual duty
would be further discussed in the next part, Chapter 4.8.1.

Production of Hydrogen via Syngas Route 4-26


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.8.1 Heat Exchanger Design Considerations

Shell and tube heat exchanger which is the most commonly used basic heat exchanger
configuration in the process industries is selected because it provides a comparatively large
ratio of heat transfer area to volume and weight and it is mechanically rugged enough to
withstand normal shop fabrication stresses and normal operating conditions. Also, it can be
easily cleaned and components susceptible to failure (gaskets and tubes) can be easily
replaced.

According to the heat exchanger network design, there are 3 heat exchangers designed to cool
down the HTS outlet stream to the cooled LTS feed stream. I will be designing the heat
exchanger which is used to cool HTS outlet and to heat up SMR feed.
Split ring internal floating head heat exchanger is selected for this heat exchanger. It can be
used for liquids that foul as the tubes and bundle can be removed from shell for cleaning or
repairing without removing the floating head cover. Since the HTS outlet is the stream that
causes more fouling than the SMR feed, I have chosen to use HTS outlet in the tube side, and
SMR feed in the shell side.

4.8.1.1 Physical properties extraction

The physical properties of the two streams are extracted from Hysys. The average values are
used for the design. Where duty, Q = 4.622 MW.

HTS outlet inlet outlet mean


temperature (o C) 263.3 234.3 248.8
specific heat(kJ/kg-C) 2.637 2.622 2.629
thermal conductivity (W/m-C) 0.1123 0.1072 0.1097
density(kg/m3) 7.444 7.893 7.661
viscosity(cp) 0.01759 0.01700 0.01735

Production of Hydrogen via Syngas Route 4-27


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

SMR feed
temperature (o C) 218 253.3 235.7
specific heat(kj/kg-C) 2.326 2.342 2.334
thermal conductivity (W/m-C) 0.04511 0.0491 0.04712
density(kg/m3) 12.60 11.57 12.09
viscosity(cp) 0.01424 0.01535 0.01480

4.8.1.2 Determination of overall heat transfer coefficient

After iterations, the overall heat transfer coefficient was U=540.1 W/m2oC. For an exchanger
of this type with light gases as hot gas and methane and water vapor as cold gas, the overall
heat transfer coefficient according to Table 12.1 of Coulson and Robertson’s Chemical
Engineering Design textbook falls in the acceptable region.

4.8.1.3 Exchanger type and dimensions

∆Tm = Shell can be carbon steel. Tube can be stainless steel due to H2 pitting. The HTS outlet
is dirtier than the SMR feed, therefore put the HTS outlet through the tubes and the SMR feed
through the shell.
(Th,in − Tc,out ) − (Th ,out − Tc ,in ) (263.3 − 253.3) − (234.3 − 218)
∆TLMTD = = = 12.89 Ο C
 Th,in − Tc ,out   263.3 − 253.3 
ln   ln  
 Th,out − Tc ,in   234.3 − 218 

263.3 − 234.3 253.3 − 218


R= = 0.8215 , and S= = 0.7792
253.3 − 218 263.3 − 218

From Fig 12.19, Ft = 0.70 , which is acceptable.

∆Tm = 0.70 × 12.89 = 9.02 Ο C

Production of Hydrogen via Syngas Route 4-28


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.8.1.4 Heat transfer area

Q 4.4622 × 10^ 6
AΟ = = = 915.3m 2
U × ∆Tm 540.1 × 9.02

4.8.1.5 Layout and tube size

A split-ring floating head exchanger is used for efficiency and ease of cleaning. Use
19.00mm outside diameter, 15.00mm inside diameter, 5m long tubes on a triangular
23.80mm pitch.

4.8.1.6 Number of tubes

Area of one tube(neglecting tube sheets thickness) = π × 19.00 × 10 −3 × 5 = 0.2985m2


Number of tubes = 915.3 / 0.2985 = 3066
So, for 2 passes, tubes per pass = 3066 / 2 = 1533
(Check for tube-side velocity to see if reasonable)
Tube cross-sectional area = ( π /4)(15 × 10-3)2 = 0.0001767 m2
Thus, area per pass = 1533 × 0.0001767 = 0.2709m2
Volumetric flow = (2.074 × 10^5/3600) × (1/7.661)=7.52 m3/s
Tube side velocity, u t = 7.52 / 0.2709=27.76 m/s

4.8.1.7 Bundle and shell diameter

For 2 tube passes, K1= 0.249, n1= 2.207,


So, Db = 19.0 × ( 1533 / 0.249 )1/ 2.207 = 1.36 m
For a split-ring floating head exchanger the typical clearance is 20 mm, so the inside shell
diameter, Ds= 1.36 + 0.02 = 1.38 m

Production of Hydrogen via Syngas Route 4-29


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.8.1.8 Tube-side heat transfer coefficient

7.661 × 27.76 × 15 × 10 −3
Re = = 183,801
0.01735 × 10 −3
2.629 × 10 3 × 0.01735 × 10 −3
Pr = = 0.42
0.1097
L 5000
= = 333
Di 15.00
From figure 12.23, jh = 0.045
Nu = 0.023 × (183801) 0.8 (0.42) 0.33 = 281

 0.1097 
hi = 281 ×  −3 
= 2049 W/m2C
 15.00 × 10 

4.8.1.9 Shell-side heat transfer coefficient

Take baffle spacing to be Ds /5 = 1.38/5 = 0.276 m = 276mm. This spacing should give good
heat transfer.
 23.80 − 19.00 
1380 × 0.4 × 1380 = 151 × 10 mm = 0.151m
3 2 2
As = 
 23.80 
 1.27 
(23.80 − 0.785 × 19.00 ) = 18.76mm
2 2
D e= 
 19.00 
Volumetric flow rate = 1.835 × 105/3600/12.085 = 4.217m3/s
Shell-side velocity, us= 4.217/0.151 = 27.9 m/s
1.835 × 10 5
× 0.0188
Re = 3600 × 0.151 −5 = 4.274 × 105
1.48 × 10
2.334 × 10 3 × 0.01480 × 10 −3
Pr = = 0.733
0.04712

From Fig 12.29, jh=0.45


0.04712
hs = ( ) × 0.45 × 4.274 × 10 5 × 0.733 0.33 = 4.36 × 10 5 W/m2C
0.01876

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CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.8.1.10 Overall coefficient

 19 
19 × 10 −3 × ln 
1  1 1  19  15  + 1 + 1
= +  +
U 0  2049 1249  15 2 × 55 5678.6 436000

U 0 =540.1W/m2 oC.

4.8.1.11 Pressure drop

5
∆Pt = 2 × (8 × 0.045 × + 2.5) × (0.5 × 7.661 × 27.7512 ) = 722739 Pa = 722kPa
0.015

From Fig 12.30, jf = 0.028

1.37 4.83 12.085 × 27.9 2


∆Ps = 8 × 0.028 × × × = 185418 Pa = 185kPa
0.0188 0.5 2

Production of Hydrogen via Syngas Route 4-31


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.9 CONCLUSION

The HTS reactor designed has determined the parameters as shown:

1. Conversion of CO from 13.34% dry basis to a composition of 3% dry basis


2. The mole fraction of the outlet of HTS
3. The weight of catalyst needed for the reaction.
4. Pressure drop of the reactor.
5. The dimensions of the reactor were also calculated, namely length of reactor, diameter
of reactor and thickness of reactor.
6. The cost of the catalyst needed was calculated, as well as the cost of the vessel.

These give a good idea on the design of the HTS reactor as well as the cost of building the
reactor.

Production of Hydrogen via Syngas Route 4-32


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.10 NOTATIONS

νi : stoichiometric coefficient of species i

µi : chemical potential of species i


n : number of moles
G : specific gibbs energy
ε : reaction coordinate
T : temperature of system
P : pressure of system
Gt : total gibbs free energy

∏ i
: product over all species i

ν : total stoichiometric number


(− rCO ) : reaction rate in lb moles CO converted/(lb catalyst/hr)

ψ : activity factor
k : rate constant
K : equilibrium constant
yi : mole fraction of species i

ρb : bulk density of catalyst (lb/ft3)


T : temperature in K
F : component molar flow rate
W : weight of catalyst
cp,j : heat capacity of component j
t : minimum thickness of wall without corrosion
P : design pressure of the reactor vessel
R : internal radius of shell without corrosion
S : maximum allowable stress value
E : joint efficiency (assume = 1)
Dp : characteristic length of pellet (ft)
G : mass flux (lb/s)
µ : average viscosity of fluid (cP)

Production of Hydrogen via Syngas Route 4-33


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

NRe : reynolds number


L : length of reactor
D : diameter of reactor
dc : diameter of cylindrical catalyst pellet (ft)
hc : height of cylindrical catalyst pellet (ft)
ρb : bulk density of catalyst pellet (70 lb/ft3)
ε : voidage
fk : friction factor
ρf : density of fluid (lb/ft3)

Production of Hydrogen via Syngas Route 4-34


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.11 REFERENCES

1. H.F. Rase, Chemical Reactor Design for Process Plants, Vol 2, New York Wiley,
1977
2. J.M. Smith, H.C. Van Ness, M.M. Abbott, Introduction to Chemical Engineering
Thermodynamics 7th ed, 2005
3. H.F. Rase, Chemical Reactor Design for Process Plants, Vol 1, New York Wiley,
1977
4. R. Q. Barr, A Review of Factors Affecting the Section of Steels for Refining and
Petrochemical Applications, Climax Molydenum Co., Greenwich, Conn., 1971
5. C.H. Samans, Hydrocarbon Process., 42(10), 169 and (11) 241, 1963
6. H. M. Spencer, Industrial Engineering Chemistry, Vol 40, pg 2152-2154, 1948
7. K. K. Kelley, U.S Bur.Mines Bull. 584, 1960
8. L. B. Pankratz, U.S. Mines Bull. 672, 1982

Production of Hydrogen via Syngas Route 4-35


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

4.12 APPENDICES

Appendix 4.12.1

T= input('Please enter initial temperature for reactor in K:');


F= 2.2*15797; %flowrate in lbmol/hr
yco= 0.080035;
yh2o= 0.400173;
yco2= 0.049934;
yh2= 0.43523;
yc2h6= 0.001975;
ych4= 0.031995;
yn2= 0.000658;

Fco= F*yco;
Fh2o= F*yh2o;
Fco2= F*yco2;
Fh2= F*yh2;
Fc2h6= F*yc2h6;
Fch4= F*ych4;
Fn2=F*yn2;

k=exp(15.95-4900/T);
K=exp(-4.33+4578/T);
rate=4*k*(yco*yh2o-yco2*yh2/K)/(379*70);

Fco1= Fco -rate*200;


Fh2o1= Fh2o-rate*200;
Fco21= Fco2 + rate*200;
Fh21= Fh2 +rate*200;

cpco= (3.376+(0.557/10^3)*T -(0.031*10^5)*T^(-2))*8.314;


cpc2h6=(1.131+(19.225/10^3)*T-(5.561/10^6)*T^2)*8.314;
cph2o=(3.47+(1.45/10^3)*T +(0.121*10^5)*T^(-2))*8.314;
cpco2=(5.457+(1.045/10^3)*T -(1.157*10^5)*T^(-2))*8.314;
cph2=(3.249+(0.422/10^3)*T +(0.083*10^5)*T^(-2))*8.314;
cpn2=(3.28+(0.593/10^3)*T +(0.04*10^5)*T^(-2))*8.314;
cpch4=(1.702+(9.081/10^3)*T -(2.164/10^6)*T^2)*8.314;

deltaa = 5.457 + 3.249 - 3.376 - 3.470;


deltab = (1.045 + 0.422 - 0.457 - 1.450) * 10^-3;
deltad = (-1.157 + 0.083 - (-0.031) - 0.121) * 10^5;

integral =(deltaa * 298.15 * ((T/298.15) - 1) +


(deltab/2)*(298.15^2)*(((T/298.15)^2)-1) + (deltad/298.15)*(((T/298.15) -
1)/(T/298.15)));

dHco = -41166 + 8.314 * integral;

dT = ((rate * 200) * (-
dHco))/(Fco*cpco+Fh2o*cph2o+Fco2*cpco2+Fh2*cph2+Fc2h6*cpc2h6+Fn2*cpn2+Fch4*
cpch4);

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CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

T1 = T + dT;

yco1 = Fco1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh2o1= Fh2o1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yco21= Fco21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh21= Fh21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);

ydryco= (yco1/(1-yh2o1));

i=1;

while ydryco>0.03,

k=exp(15.95-4900/T);
K=exp(-4.33+4578/T);
rate=4*k*(yco*yh2o-yco2*yh2/K)/(379*70);

k=exp(15.95-4900/T1);
K=exp(-4.33+4578/T1);
rate1=4*k*(yco1*yh2o1-yco21*yh21/K)/(379*70);

rateavg= (rate+rate1)/2;

Fco = Fco1;
Fh2o = Fh2o1;
Fco2 = Fco21;
Fh2= Fh21;

Fco1= Fco -rateavg*200;


Fh2o1= Fh2o-rateavg*200;
Fco21= Fco2 + rateavg*200;
Fh21= Fh2 +rateavg*200;

cpco= (3.376+(0.557/10^3)*T1 -(0.031*10^5)*T1^(-2))*8.314;


cpc2h6=(1.131+(19.225/10^3)*T1-(5.561/10^6)*T1^2)*8.314;
cph2o=(3.47+(1.45/10^3)*T1 +(0.121*10^5)*T1^(-2))*8.314;
cpco2=(5.457+(1.045/10^3)*T1 -(1.157*10^5)*T1^(-2))*8.314;
cph2=(3.249+(0.422/10^3)*T1 +(0.083*10^5)*T1^(-2))*8.314;
cpn2=(3.28+(0.593/10^3)*T1 +(0.04*10^5)*T1^(-2))*8.314;
cpch4=(1.702+(9.081/10^3)*T1 -(2.164/10^6)*T1^2)*8.314;

integral = (deltaa * 298.15 * ((T1/298.15) - 1) +


deltab/2*298.15^2*((T1/298.15)^2-1) + deltad/298.15*(((T1/298.15) -
1)/(T1/298.15)));

dT = ((rateavg * 200) * (-
dHco))/(Fco*cpco+Fh2o*cph2o+Fco2*cpco2+Fh2*cph2+Fc2h6*cpc2h6+Fn2*cpn2+Fch4*
cpch4);

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CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

yco = yco1;
yh2o = yh2o1;
yco2 = yco21;
yh2 = yh21;

yco1 = Fco1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh2o1= Fh2o1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yco21= Fco21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh21= Fh21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);

ydryco= yco1/(1-yh2o1);

x(i) = i*200/2.2;
y(i) = T;
a(i) = ydryco;

T = T1;
T1 = T + dT;
i= i + 1;
end

Wt=i*200/2.2;

fprintf('mass of catalyst is %f kg.\n',Wt);


fprintf('outlet temperature of HTS is %f K.\n',T1);
fprintf('mol fraction of CO is %f .\n',yco1);
fprintf('mol fraction of H2O is %f .\n',yh2o1);
fprintf('mol fraction of CO2 is %f .\n',yco21);
fprintf('mol fraction of H2 is %f .\n',yh21);
fprintf('mol fraction of N2 is %f .\n',yn2);
fprintf('mol fraction of CH4 is %f .\n',ych4);
fprintf('mol fraction of C2H6 is %f .\n',yc2h6);
fprintf('mass flowrate in lb/hr is %f .\n',F);

plot (x,y);
plot (x,a);

Appendix 4.12.2

mass = 281609.79; %mass of catalyst in lbs


flowrate = 456300; %flowrate in lbs per hour
u1 = 0.01999; %inlet viscosity in cp
u2 = 0.02118; %outlet viscosity in cp
pf = 0.4125; %density of feed in lbs per feet3
u = (u1+u2)/2;
V = 1.2*mass/70;

for i=1:600;
L = i*0.1;
D = 2*((V/(pi*L))^0.5);
AR = L/D;
area = pi*(D/2)^2;
G = flowrate/area;

Production of Hydrogen via Syngas Route 4-38


CN 4120: Design II
Team 32: Ong Song Kun (U046829M) HTS Unit Design Report

Dp = 0.25/12;
Nre = Dp*G/(2.42*u);
fk = 1.75+150*(0.555)/Nre;
dPft = L*((fk*G^2/(Dp*pf*32.17*(3600^2)))*0.555/(0.445^3));
dPsi = dPft/(12^2);
dPbar = dPsi/14.7;

x(i,1) = AR;
x(i,2) = dPft;
x(i,3) = dPsi;
x(i,4) = dPbar;
x(i,5) = G;

end
plot(x(:,1),x(:,4));

Appendix 4.12.3

mass = 281609.79; % mass of catalyst in lbs


AR= 3.497; %AR
P = 454.2; %pressure in psi
S = 13.1; %maximum allowable stress value in kips per inch square

V = mass*144*12/70;
E = 1;
D = (4*V/(pi*AR))^(1/3);
L = D*AR;

t=P*(D/2)/(S*1000*E-0.6*P);
D=D*0.0254;
L=L*0.0254;
fprintf ('t= %f inches \n',t);
fprintf ('D= %f metre \n',D);
fprintf ('L= %f metre \n',L);

Production of Hydrogen via Syngas Route 4-39


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

Chapter 5 : LOW TEMPERATURE SHIFT REACTOR


5.1 INTRODUCTION

The water shift reaction usually occurs in an fixed bed adiabatic system with the presence of
a catalyst to speed up the reaction rate. In an adiabatic system, CO slip is determined by the
exit temperature of the shift converters, because low temperatures results in low equilibrium
levels of CO, as the following exothermic process is taking place:

CO + H2O ⇌ CO2 + H2 ∆H = -41.2kJ/mol (5-1)

On the other hand, favorable kinetics occurs at higher temperatures. Either a high steam-to-
gas ratio or low temperature can be used to improve CO conversion percentage, but that also
correspondingly contribute to higher capital and operation cost. Hence there is a tradeoff
between CO conversion percentage and costs.

Fig.1 Typical CO variation in high temperature and low temperature shift catalyst beds
[Frank, 2003a]

Conversion in a single high-temperature-shift(HTS) converter is equilibrium limited. Since


this reaction is exothermic, the rise in temperature as reaction proceeds will eventually not
favor further reaction. This limitation can be overcome by employing a second converter, the
low-temperature-shift (LTS) converter after the HTS converter. Usually an inter-bed cooling
process is employed between the two converters to keep the reaction occurring at low
temperature in the second converter. A knock-out drum is then employed to condense and
remove all water prior to feeding into the pressure swing adsorption (PSA). This part of the
design project presents detailed chemical engineering design of a LTS converter and the
knock-out drum.

Production of Hydrogen via Syngas Route 5-1


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

Fig.2 LTS converter in the HYSYS environment

5.2 LTS DESIGN CONSIDERATIONS


5.2.1 Current Status
Carbon monoxide exits the HTS converter with a molar fraction of 0.03(dry basis) at 420oC.
The stream, with a molar flow of 11354kmol/h, is then cooled to bring the temperature down
to 220oC before feeding into the LTS converter. Molar composition of the feed is illustrated
in the following diagram.

Fig.3 Molar compositions of feed into LTS converter

The outlet composition was automatically generated using Hysys, using the rate equation
associated with this reaction (and catalyst type). However, it should be noted due to its
iterative nature, Hysys could not obtain a value closer to that of the exact situation than
Matlab. Hence, there is still a need to carry out interations (based on the same rate equation)
in the Matlab environment. A comparison between results calculated from both programs will
be made in latter section.

Production of Hydrogen via Syngas Route 5-2


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.2.2 Kinetics of Low-Temperature Water-Gas-Shift (LTWGS)

Equation (5-1) may be represented in the following form

A+B ⇌ C+D (5-2)

where A, B,C and D are CO, H2O, CO2 and H2 respectively

Rase (1977) has come up with the following equation for application to the shift conversion:

(5-3)

Where Xi = the dimensionless concentration of component i (Ci/Cref)


k = rate constant
= exp (12.88 -1855.6/T) for copper-zinc catalyst
K = equilibrium constant
= exp (-4.72 + 8640/T) for 760 ≤ T ≤ 1060
P = pressure, atm
(-rco) = rate, lb moles CO converted/(lb catalyst)(hr)
T = temperature, K
yj = mole fraction of component indicated
ρb = catalyst bulk density, lb/cu ft
ψ = activity factor for the copper-zinc catalyst

Copper-zinc catalyst ψ = 0.86 + 0.14P for P ≤ 24.8


= 4.33 for P ≥ 24.8

Production of Hydrogen via Syngas Route 5-3


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.2.2.1 Assumption made for equation (5-3) :

This equation represents the activity level characteristic of mid-life of the catalyst.
These rate constants have been expressed on the basis of a reasonable “lined-out” activity that
the catalyst would maintain for a considerable time provided operating errors which cause
deactivation do not occur.

Multiplying the rate equation by ρb , we obtain the rate of reaction in units of moles of CO
converted per unit volume of catalyst per second, and converting the units to S.I units, we
obtain the following equation

(5-4)
Where

(5-5)
The pre-exponential factor ko includes the diffusion effect as given by the catalyst
manufacturer (Rase, 1977).

Production of Hydrogen via Syngas Route 5-4


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.2.3 LTS Catalyst

From (5.3), it is important to decide the catalyst which we are using for the LTS shift.
Copper-Zinc Oxide supported on alumina will be taken as the catalyst for our design and its
specifications will be used for the calculations.

Copper-Zinc oxide offers the thermodynamic advantage of a lower operating temperature for
the exothermic reaction in eq. (5-1)

Characteristics of the catalyst assumed for this design are as follows:

Catalyst Type Copper-Zinc Oxide supported on alumina


o
Maximum Operating Temperature ( C) 260 - 288
Tablet Size (in.) ¼ x 1/8
Bulk Density (lb/cu ft) 90
Particle Density ($/cu ft) 155
Cost ($/cu ft) 75
Catalyst Poison Sulfur and halogen compounds, as well as
unsaturated carbons
Catalyst life 2-3 yr

Fig.4

Production of Hydrogen via Syngas Route 5-5


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.2.3.1 Characteristics of the industrial LTS catalyst

The low-temperature shift catalyst is usually a mixture of copper oxide and zinc oxide in a
ratio between 1:1  1:2, with alumina added in place of some of the zinc oxide. In addition,
promoters such as Cr2O3, MnO, or some metal oxides have been used. Chromium oxide has
been used in place of alumina. Preparative procedures on the whole are more critical for the
LTS catalyst than for the HTS catalyst.

5.2.3.2 Preparation

Preparative procedures are much more critical for the LTS catalyst as compared to the HTS
catalyst. Coprecipitation of the metals as metal nitrates are carried out via pH adjustment with
ammonium bicarbonate. The oxides formed in this way are intimately intermixed by this
procedure, which is essential for high activity and stability. It has been suggested that ZnO in
excess can protect the copper content from inadvertent sulfur poisoning. Aluminum oxide
also serves as a stabilizer for the copper, preventing it from being sintered easily. Thus we
can see that the manufacture of these LTS catalysts involve great skill and refined proprietary
techniques.

Since the LTS catalyst is pyrophoric, it must be sequested during system shutdown when
only air flows through the system.

5.2.3.3 Supply

Catalyst suppliers usually offer thorough instructions for the start-up, catalyst reduction,
operation and shutdown for the particular catalysts purchased. Instructions for catalyst
reduction and start-up are particularly critical, since excessive temperatures must be avoided.

Production of Hydrogen via Syngas Route 5-6


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

One of the many suppliers for the LTS catalyst is Haldor Topsoe. Listed below are
properties of an example of the LTS catalyst produced from this company.

http://www.topsoe.com/

5.2.3.4 Deactivation of LTS Catalyst

(I) Poisons
Common poison of the LTS catalyst are sulfur and chlorine compounds. Sulfur compounds
such as H2S are removed in the ZnO adsorber beds prior to feeding into the steam-methane
reformer. However there could exist times of upset such as short-periods of high-sulfur feed.
In such instance, break-through sulfur will occur and pass to the HTS converter. There is a
high possibility the HTS catalyst will be able to safely adsorb the H2S and protect the LTS
bed. In some circumstances, sulfur may still get into the LTS. It is for this reason that LTS
catalysts contain excess ZnO so that upper portion of the bed can serve as a sulfur guard. Zinc
sulfide forms for the early part of the bed but further down the bed, sulfur in the form of H2S
is chemisorbed, the extent of this happening depends on the operating operations.
Consequently, deactivation of actives sites will take place.

Chloride compounds are a major and permanent poison of LTS catalyst, and worth a mention
despite the fact that no chloride compounds are involved in this design project.

Production of Hydrogen via Syngas Route 5-7


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

CuCl and ZnCl2 are formed and they can cause copper crystal growth (sintering) and
significant loss of catalyst activity. Ways to tackle the problem of choride poisoning involve
installing a bed of chlorine adsorbent (e.g. CaO/ZnO or alkalized alumina) upstream of the
ZnO adsorbent bed prior to the reformer, another bed is placed above the LTS catalyst,
composed of a chlorine adsorbent as well.

(II) Sintering

Excessive temperature can result in sintering. Very small crystallites of copper are
thermodynamically favored to coalesce into large crystals and thus produce a less active
catalyst due to low porosity overall. Despite the fact that these crystallites are stabilized by
the associated ZnO and also alumina, this protection is destroyed at elevated temperatures.
Inlet operating temperatures for LTS between 175-275oC have been suggested, but it is
always encouraged to operate at the lowest temperature possible, since sintering is a
phenomenon related to both time and temperature. However, there is a lower temperature
limit for the operating condition in the LTS converter, to avoid the any condensation of the
steam we use in the low temperature shift reaction, as any condensation in the pores can
result in catalyst damage. It is often suggested that the lowest temperature should be no lower
than 20oC above the dewpoint.

5.2.3.5 LTS catalyst in operation

A common practice of some hydrogen-producing companies is to increase temperature


during a LTS operating cycle to overcome deactivation of the catalyst. This will however,
increase the growth of the crystals and shorten the life of the catalyst. In the lower regions of
temperature, sintering rate is very low but this increases as temperature is raised. Ultimately,
deactivation rate becomes significant and the catalyst activity will suffer. The higher the bed
temperature reached, the more critical temperature control becomes, particularly if the
process gas is introduced after the bed reaches operating temperature. Sudden rapid rise in
temperature can damage the catalyst.

Reducing gas of H2 mixed with N2 or with natural gas is usually recommended for LTS
catalyst to keep the catalyst in the reduced form.

Production of Hydrogen via Syngas Route 5-8


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.2.3.6 Assumptions made for LTS Catalyst

The following assumptions have been made for the derivations of the differential equations
which characterize the pellet mass and heat balance
1. The Copper Zinc catalyst pellet particles have a homogenous porous structure
2. Mass transfer within the catalyst particles occurs by diffusion only which may be
expressed by a constant effective diffusion coefficient D, and rate of intraparticle
diffusion is described by Fick’s Law
3. Conduction is responsible for the thermal transfer within catalyst particles and
effective thermal conductivity λe is used with the Fourier’s law, to describe the
intraparticle heat conduction
4. Both mass and heat transfer within the catalyst pellets only take place in the radial
direction

5.2.3.7 Mass balance on the Copper-Zinc catalyst pellet

Dimensionless steady state material balance for component I over a shell of dimensionless
thickness dw ( where w is the dimensionless radial coordinate, z/Rp) is given by:

(5-6)
where

(5-7)

φi is Thiele’s modulus of the pellet, for component i and is defined as

(5-8)
and

(5-9)

Production of Hydrogen via Syngas Route 5-9


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

γ is the dimensionless activation energy, defined as

(5-10)

Equation (5-10) is a second order differential equation of the boundary value type having two
split boundary conditions:
At ω = 0

(5-11)
At ω = 1

(5-12)
where i = A,B,C,D

5.2.3.8 Heat balance on the Copper-Zinc catalyst pellet

The dimensionless steady state enthalpy balance over the shell of dimensionless thickness
dω is given by

(5-13)
Where βi is the thermicity factor of the pellet based on component I, defined as

(5-14)

The boundary conditions being:


At ω = 0

(5-15)

At ω = 1

(5-16)

Production of Hydrogen via Syngas Route 5-10


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

The non-isothermal effectiveness factor for a spherical particle the non-isothermal


effectiveness factor η is defined as:

(5-17)

In dimensionless form the above equation becomes

(5-18)

It can also be written as

(5-19)

Production of Hydrogen via Syngas Route 5-11


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.2.4 Modeling the converter

5.2.4.1 Assumptions made for the converter

The heterogeneous model is developed in terms of bulk variables with the effectiveness
factor introduced to account for the diffusional limitations. The assumptions made for the
overall reactor model are as follows:
1. There is uniform distribution of gas flow velocity inside the converter
2. The reactor is studied under steady state conditions
3. The radial distribution of the temperature and concentration of the different
components inside the converter is uniform, i.e. the model is one-dimensional
4. Heating and mass diffusion in the longitudinal direction are negligible considering the
very high gas velocities at which the reactor is operated, i.e. axial dispersion is
negligible
5. The pressure drop across the reactor is negligible compared with the total pressure of
the reactor

5.2.4.2 Reactor mass balance

For the bulk gas phase, the rate of reaction is formulated in terms of the mole fractions Yi
instead of the dimensionless concentrations Xi (as in the catalyst pellets equations). This is a
more convenient approach as the total number of moles is constant, while the volumetric gas
flowrate is changing due to the change of temperature.

At steady state, a component mass balance on CO over an element of catalyst bed of


thickness dl and a cross sectional area Ai , with a constant total molar flow rate nT , gives

(5-20)
where nA is the molar flow rate of component A, and the rate of reaction is given by (Rase,
1977)

(5-21)

Production of Hydrogen via Syngas Route 5-12


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

In a dimensionless form, the equation becomes

(5-22)

Where z’ = I/L and

KB is the temperature dependent equilibrium constant which is defined as (Borgars and


Campbell, 1974):

(5-23)

where yB = TB/Tref and (CO2), (H2), (CO), (H2O) are the partial pressures or fugacities for the
different species in equilibrium.
The boundary condition at the inlet of the reactor is at z’=0

(5-24)

5.2.4.3 Reactor mass balance


At steady state, the heat balance equation is

(5-25)
In a dimensionless form, the equation will be

(5-26)
where

(5-27)
The boundary condition is at z’= 0

(5-28)
The bulk phase temperature can also be computed from the bulk phase concentration by
making a cumulative heat balance over any reactor length

(5-29)

Production of Hydrogen via Syngas Route 5-13


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

Therefore, it is sufficient to integrate (5-22). There is no need to integrate equation (5-27)


along the length of the reactor, equation (5-29) can be used instead.

From stoichiometry, at any depth of the reactor, the concentration of CO2, H2O, H2 can be
expressed in terms of the bulk concentration as follows:

(5-30)

Where I = B, C, D and a =-1 for reactants and a = +1 for products.

5.2.4.4 Transport parameters

Viscosity and thermal conductivity


The viscosity µ of the fraction, designated by subscript x at a density ρ and temperature T is
given in terms of a reference fluid, designated by subscript o. The equation is

(5-31)
where

(5-32)

With M as the molecular weight and To, ρο defined by the ratios

(5-33)
and

(5-34)

fx,o and hx,o are scaling ratios, which are in general

(5-35)
and

(5-36)

Production of Hydrogen via Syngas Route 5-14


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

The subscript c denotes the critical value and the superscript * denotes reduction of the
variables by the critical value. The functions θ and φ are the shape factors expressed in

terms of Pitzer acentric factor, ω , via functions of the form

(5-37)
and

(5-38)

where F and G are universal functions reported for example, by Leach et al. (1968) and Ely
and Hanley (1981). The thermal conductivity λ is also evaluated through the same procedure
(Ely and Hanley, 1981)

Prandtl number
The prandtl unmber Pr is computed as

(5-39)

Diffusion coefficients
The binary diffusion coefficient of each component is computed by the relation

(5-40)

where vi are the values of the atomic and structural diffusion-volume coefficients (Perry et
al,1984)

The value of the diffusion of each component in the mixture is calculated by the relation
(Bird et al. 1960)

(5-41)

where Yi = mole fraction of each component, Dij = the binary diffusion coefficient, and Di,mix
= diffusion coefficient for each component in the mixture.

Production of Hydrogen via Syngas Route 5-15


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

External mass and heat transfer coefficients


Correlations for both mass and heat transfer coefficients kg and h are found empirically from
the mass and heat transfer J-factor (JD and JH) correlations, which are defined as

(5-42)
and

(5-43)
The values for JD and JH are almost equal and are computed as a function of the Reynolds
number:
JD = JH = 0.989 Re-0.41 for Re>350
= 1.820 Re-0.51 for Re<350 (5-44)

where, Re = Reynolds number = Gdp / µ

The external mass transfer in the pellet equation takes the form

(5-45)

and the external mass transfer coefficient is calculated by the relation

(5-46)

where RG= the universal gas constant and T = average temperature for the catalyst bed.

Production of Hydrogen via Syngas Route 5-16


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.3 DESIGN CONDITIONS

5.3.1 Temperature

Inlet temperature has been set at 220oC, a temperature which is low enough to prevent the
sintering of the LTS catalyst, and high enough to prevent any condensation of steam taking
place, damaging the catalyst as a result. Referring to (5-3), as pointed out by Rase, it can
shown that rate doubles for a rise of 200oC for the LTS catalyst. By using around 232oC as an
approximate maximum for design, we can have the opportunity to raise the temperature to
compensate for a 50% loss in activity for the LTS catalyst.

The rate data in (5-3) is based on activities of the catalyst at mid life, so it is expected that the
unit will perform better than the design at the outset. Designed outlet CO values can be kept
by adopting the strategy of increasing temperature over a long period of time. This is done in
view of the fact that activity of catalyst will decline towards the last half of its life. Increasing
temperature further however, can result in sintering of the catalyst sintering, leading to lower
activity of the catalyst. Hence, increasing temperature in such case does not remedy the
situation at all.

5.3.2 Pressure

The LTS converter will be operating at the pressure of 24.86 bar. Much care has to be taken
to prevent a high pressure drop across the LTS converter. This is to facilitate a high enough
pressure for the Pressure Swing Adsorption unit that follows the knock-out drum.

5.3.3 Steam to CO ratio

As suggested by Rase (1977), Steam to CO ratio should be in the range of 4:1 and above.
Economic analysis on design studies has to be done before the optimum value can be
obtained. The disadvantages with using a higher steam rate will be that of higher flow rates
and larger diameter equipment.

Production of Hydrogen via Syngas Route 5-17


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

For the HTS unit, inlet’s molar flow of H2O and CO is as follows:

Species Molar flow (kmol/hr)


H 2O 6326.9
CO 1265.6

The Steam to CO ratio employed for the HTS case is (6326.9/1265.6) = 5

For the LTS unit, inlet’s molar flow of H2O and CO is as follows:

Species Molar flow (kmol/hr)


H 2O 5374.4
CO 313.1

The Steam to CO ratio for this case is (5374.4/313.1) = 17.2

Explanation and justification for the high ratio used for LTS:

Both CO and H2O react to form CO2 and H2. So it is understood that both the molar flow of
CO and H2O will decrease once they go through the first water-gas-shift reaction in the LTS
converter. However, CO gets converted to a much greater extent (from 1265.6kmol/h to
313.1kmol/h) as compared to H2O. Given a much greater change in the denominator of
(H2O/CO), we can hence expect an inevitable high Steam to CO ratio for the inlet feed of the
LTS converter.

Drawing steam from the feed to the LTS converter just to meet a H2O:CO ratio of around 4:1
will be an unwise move as this will give rise to greater need for extra units prior to feeding
into the LTS converter to condense the steam and then remove the liquid phase. Higher steam
does have the advantage of the driving the water-gas-shift equation to the right, producing
more of the products. However as mentioned, the drawback of higher steam content will be
bigger equipment needed to accommodate a higher volumetric flow.

Production of Hydrogen via Syngas Route 5-18


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.3.4 Design Procedure for LTS outlet compositions and Mass of Catalyst used

The design procedure suggested by Rase(1977) has been adopted and is as follows:

Component Mole Balance


∆W(-rCO) = (-∆FCO) (5-47)
FCOi+1 = FCOi – (-∆FCO) (5-48)
FCO2i+1 = FCO2i + ∆FCO2 (5-49)
Where i designates increment number

Heat Balance
Heat of reaction is based on the known inlet temperature of the increment
∑FjCpj(Ti+1 – Ti) = (-rCO)(- ∆HCO)Ti∆W = (-∆FCO)(- ∆HCO)Ti (5-50)

Algorithm principle
Basis: An ∆W of 200lb can never cause a ∆T greater than 1o, as pointed out by Rase(1977).
An increment size of 1o is then selected and the change in molar quantity (∆X) of a specie i.e
CO can be calculated for each increment. Algorithm is run with using n steps(cycles), the
number of steps required to reach target amount of CO in the outlet. With every increment
step involving 200lb of catalyst, total amount of catalyst can then calculated using n x 200lbs

The following algorithm has been set up:


1. Calculate (-rCO) at inlet conditions to increment, i.
2. Calculate (-rCO)avg = (-rCO)i + [(-rCO)i – (-rCO)i-1]/2 (skip for i = 0)
3. Calculate new flow rates: Fi+1 = Fi ± ( −ro) ∆W
4. Calculate Cp and (-∆HCO) @ Ti
5. Calculate ∆T from (5-50)
6. Ti+1 = Ti + ∆T
7. yi+1 = Fi+1/(FT)i

The amount of catalyst, including outlet compositions have been worked out with this
algorithm in MATLAB. Relevant codes for this portion have been attached in Appendix A.

Production of Hydrogen via Syngas Route 5-19


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.3.5 LTS outlet compositions and Mass of Catalysts used

Results of our previous algorithm are as follows:

Mole Outlet
Fraction kmol/hr
CO 0.00338 53.41
H2O 0.32347 5114.12
CO2 0.12660 2001.53
H2 0.51192 8093.44
C2H6 0.00066 10.40
CH4 0.03200 505.87
N2 0.00198 31.22

Mass flowrate in kmol/hr 15810


Mass of LTS catalyst used(kg) 34720
Outlet T (celsius) 239.3

The water shift reaction occurring in the low temperature reactor changes the composition of
the syngas species and temperature of the syngas. The CO conversion efficiency ξcan be
used to show how much CO is converted into CO2 in the LTS converter.

(4-51)

ξfor our case = (313.10 – 53.41)/313.10


= 82.9%
Mol fraction of CO in dry basis = 0.5%

Fig.5 Molar compositions of inlet and outlet feed

Production of Hydrogen via Syngas Route 5-20


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

Comparison of HYSYS and MATLAB results for outlet feed molar compositions
Species HYSYS MATLAB
CO 0.003390 0.003378
H 2O 0.323482 0.323474
CO2 0.126590 0.126599
H2 0.511910 0.511919
N2 0.000658 0.000658
CH4 0.031999 0.031997
C2H6 0.001980 0.001975

As we can see from the table above, the molar compositions for HYSYS agree well with
MATLAB‘s. Conversion value of 82.9% for CO, previously calculated in the MATLAB
environment, is inputted as part of the specifications in the Conversion Reactor module under
HYSYS.

5.3.6 Design Procedure for Aspect Ratio

As an initial approach to calculating the dimension of the catalyst bed, the aspect ratio is first
derived. The aspect ratio is defined as follows:

Aspect Ratio (AR) = (Length of Bed/Diameter of bed) (4-52)

The following equations are used:

(4-53)

(4-54)

(4-55)

(4-56)

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

(4-57)

The MATLAB codes for this portion are located under Appendix A2.

Algorithm principle
For every loop in the algorithm, there is a small increment of bed diameter accompanied by a
very small increment in bed height involved. Both variables are linked based on the volume
of the catalyst used for the design. Corresponding pressure drop, followed by the aspect ratio
are generated for every cycle.
In this case, the controlled term is pressure drop, which we have fixed to be at 1 bar max.
Generating a graph displaying Aspect Ratio against Pressure-Drop, we read off the aspect
ratio which corresponds to a pressure of 1 bar-drop.

Justification for controlling pressure drop at 1 bar:


Industrially the pressure drop across the LTS converter is no more than 1 bar. A large
pressure drop is uneconomical process-wise due to the usage of a pressure-swing adsorption
unit in the downstream. Furthermore, too high a pressure drop can damage the expensive
catalyst used for LTS.

5.3.7 Results for Aspect Ratio

Fig.6 Graphs of Aspect Ratio against Pressure Drop

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

The aspect ratio which corresponds to a pressure drop of 1 bar is 1.2287.

Using this aspect ratio, the length and height of the catalyst bed can be determined in the next
section

5.3.8 Design Procedure for the dimensions of bed and thickness of vessel wall

The MATLAB codes for this portion are located under Appendix A3.

Formulas used are as follows:

Volume of bed = (Mass of catalyst used * /90) (4-58)

By using ‘90’, the bulk density of the LTS catalyst, Equation (4-58) has already taken in
account space occupied by the voids in the catalyst packing

Diameter of bed = (4 * Volume/( π * Aspect ratio))1/3 (4-59)


Length of bed = Diameter of bed * Aspect ratio (4-60)

Thickness of vessel wall


= Pressure(psi) * (Diameter/2)/(Allowable stress value*1000 – 0.6*Pressure) (4-61)

Allowable stress value is based on the material that has been used for the construction of
vessel.

For this design, low-alloy steel A387 Gr.12 has been used for the construction of the LTS
converter given its resistance to hydrogen which is existent in the process stream. The
allowable stress value for this material is given as 13.8 Kips/in2

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.3.9 Results for bed dimensions and wall thickness

Bulk Volume of Catalyst (m3) 848.71


Diameter of Catalyst Bed (m) 2.92
Length of Catalyst Bed (m) 3.59
Wall thickness (in) 0.13

For this design, a guard bed will not be considered in view of the fact there is no sulfur
content at all in our process streams. Even if there is, I am making the assumption in this case
that all sulfur poisons will be adsorbed on the catalyst in the HTS converter, hence there is no
chance for any sulfur contents to come into contact with the LTS converter.

In reality however, due to the high sensitivity of the low temperature catalyst to sulfur
poisoning, a guard bed containing zinc oxide or other guard solids is usually positioned on
top of the catalyst bed. The guideline given by Rase(1977) is that the height for a good
distribution of the catalyst will be at 100 times the diameter of the catalyst particle.

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.3.10 Allowances set for design

• Temperature
As highlighted in a previous section, I have set a design temperature of 232oC
suggested by Rase(1977), approximately 12oC higher than the intended value of
220oC, with the assumption that this will be able to compensate for 50% loss in
activity for the catalyst

• Amount of catalyst used


The amount of catalyst used will be designed with 10% extra. No references have
been found addressing this portion on the ‘extra amount of catalyst’ to use. I have
chosen a reasonable figure of 10%-extra, with the priority of bringing outlet CO
concentration down to the desired level of less than 0.5% (dry basis) in mind. Using
excessive catalyst give rise to higher catalyst cost as well as a larger reactor to
accommodate the larger volume.

New catalyst amount = 34720 * 110% = 38192kg

• Size of catalyst bed and wall thickness


Incorporating the new catalyst amount into the calculations, corresponding
dimensions for the new catalyst bed are 3.01m(diameter) * 3.70m(length)
Again, a 10% extra allowance is made for the size of bed and wall thickness.

Before After
Bed Diameter (m) 3.01 3.31
Bed Length (m) 3.70 4.07
Wall Thickness (in) 0.13 0.14

Any space that is not taken up by the catalyst, in case of an over-design, can be easily
filled up by the inert ceramic balls which are used to support the catalyst.

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.3.11 Study of controlling parameters

Pressure drop vs bed length

It is observed pressure drop increases exponentially with an increase in bed length. As


mentioned in a previous section, maximum pressure drop has been controlled at a value of 1
bar since industrially pressure drop across the LTS converters are usually not more than 1 bar.
It is evident from this graph that increasing bed length can result in an increasing increment
of pressure drop each time. This means that an infinitely long catalytic reactor can result in a
plunge of pressure drop to atmospheric pressure. Hence there is a need to control the total
amount of catalyst use as more catalyst will call for the need of larger beds.

Production of Hydrogen via Syngas Route 5-26


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.4 CHOICE OF A REACTOR BED

Fig.7 Single Adiabatic bed incorporating measurements for bed size

Since the water-gas-shift is only moderately exothermic, the single adiabatic bed will be a
suitable reactor for performing the low temperature shift.

The feed will flow downwards from the top through a bed of the LTS catalyst packed in
between layers of inert ceramic support balls, which serve in creating even flow distribution
over the entire cross section and for separating solid contaminants that may have entered the
feed. The ceramic balls in the lower region act as a support while the ones at the top region
prevent movement of catalyst particles by high-velocity gas. Alternatively, a metal grid with
holes sized somewhat smaller than this catalyst can be used in place of the ceramic balls.

Rase has pointed out that in cases where flow rates are large and pressure drop must be
minimized, large diameter short beds will come into the picture. This seems to be the case for
our design.

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.4.1 Cost estimation for the LTS converter

Material Cost for Converter


Calculation of the amount of material i.e. low alloy steel A387 has been simplified to obtain
an approximate value. Assuming two half-spherical ends (at both sides) with diameter 3.31m,
total surface area of the reactor can be calculated as follows:

Surface area of reactor = π D * L + 4π(D/2)2


= π ∗ 3.31 * 4.07 + 4π(3.31/2)2
= 76.74 m2
Given a design thickness of 0.14in (0.0035m), total volume of material required
= 76.74 * 0.0035
= 0.26859 m3

Density of the steel is around 8g/cm3 = 8000kg/m3


Hence, mass of the steel required = 0.26859 * 8000
= 2148.72kg

Cost of low alloy steel (Cr-Mo) is quoted as around USD$700 – 850/T, as stated in the book
by Coulson and Richardson. For design purpose, we will take the higher value of USD$850/T.
Hence cost of the steel required = USD$850 * (2148.72/1000)
= USD$1826.41
This calculation fails to take into account material required for additional features of the
reactor, e.g. the flanges. Hence the amount of steel, and consequently the cost of steel used
could have been much more.
An important assumption made in the calculation of this material cost is an uniform wall
thickness of 0.14inch for the reactor. This may not hold in reality as thickness can be slightly
larger in areas where a greater stress is experienced i.e. bottom of reactor to handle the weight
of the catalyst and inert ceramic balls. Cost of the inert ceramic balls will not be included in
the cost calculation. Due to the inavailability of its cost info online, another assumption is
made: Cost of the ceramic balls is assumed a total cost of not more than USD$500. In my
view, this is a fair assumption as it is well known that the LTS catalyst accounts for a
significantly large portion of the LTS converter’s total cost.

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

Catalyst cost for converter

Copper-Zinc oxide has been quoted by Rase(1977) to be approximately USD$75/ft3. Since


total bulk volume of the catalyst in this case is (84022/90) = 936ft3,
Cost of the catalyst = 936 * 75
= USD$70,200

Factoring in the inflation rate


It ought to be noted that the cost figure quoted by Rase for Copper-Zinc Oxide was 30 years.
Over these 30 years, an increase in price has in fact taken place. The same goes for the price
of the low alloy steel A387 which was last quoted back in 2005. Hence the cost for both the
catalyst and the steel required has to be adjusted to get us a better approximation to the actual
situation. The Consumer Price Index could be a good reference to account for the amount
inflation to be factored in.

Fig.8 CPI for USA from 1913-2006

An index of 100 (base case) has been assigned to the year of 1980. From year 1977 to 2008,
it is approximately a jump from index 65 to 210 in 2008 (Value for 2008 has been
approximated from the trend in the graph). From 2005 to 2008, it is probably an increment of
10 index, from 190 to 210. The adjusted total cost of the reactor is as follows:
Cost of LTS Converter(adjusted) = USD$70,200 * (210/65) + 1826.41 * (210/190) + 500
= USD$229,318

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

5.5 DESIGN OF THE KNOCK-OUT DRUM

Fig.9 Knock-out drum in the HYSYS environment

5.5.1 Working principle of the knock-out drum


The knock-out drum is basically a vapor-liquid separator drum which is in the form of a
vertical vessel into which a liquid and vapor mixture (or a flashing liquid) is fed. Within the
drum, the liquid is falls to the bottom of the vessel because of gravity and hence a separation
is achieved, the liquid phase(water for this case) is then withdrawn. The vapor, on the other
hand, travels upward at a design velocity which minimizes the entrainment of any liquid
droplets in the vapor as it exits the top of the vessel.

5.5.2 Sizing of the knock-out drum


The size of the knock-out drum will be dictated by the anticipated flow rate of vapor and
liquid from the drum. Based on the assumption that those flow rates are known, the following
sizing methodology is proposed:

(1) A vertical pressure vessel with a length-to-diameter ratio of about 3 to 4 is used, vessel is
sized to provide about 5 minutes of liquid inventory between the normal liquid level and the
bottom of the vessel (with the normal liquid level being at about the vessel's half-full level)

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

(2) The vessel diameter is calculated using the Souders-Brown equation to determine the
maximum allowable vapor velocity:

(5-62)
Where V=maximum allowable vapor velocity, m/s
ρL= liquid density, kg/m³
ρV= vapor density, kg/m³

k= 0.107 m/s (when the drum includes a de-entraining mesh pad

Then the cross-sectional area of the drum (A) is obtained from:

A, in m² = (vapor flow rate, in m³/s) ÷ (vapor velocity V, in m/s) (5-63)

And the drum diameter (D) is:

D, in m = [(4) (A) ÷ (3.1416) ] 0. 5 (5-64)

5.5.3 Results and cost estimation

The following values have been obtained from HYSYS

ρL = 993.3 kg/m3
ρV = 9.92kg/m3
Vapor mass rate = 32.17kg/s
Vapor volumetric rate = 32.17/9.92
= 3.24m3/s

V = (0.107) ((993.3-9.92)/9.92))1/2
= 1.07m/s

Cross sectional area (A) of drum = 3.24/1.07


= 3.03

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

Diameter (D) of drum = [(4 * 3.03)/3.1416]0.5


= 1.96m
Height of drum = 1.96 * 4
= 7.84m

Treating shape the knock-out drum as a cylinder with a thickness similar to that of LTS
converter,
Surface area of the knock out drum = 2 * π (1.96/2)2 + π*1.96*7.84
= 54.49m2

Low-alloy steel A387 Gr.12 has been used for the construction of the knock-out drum

Assuming a thickness of 0.14in,

Volume of A387 used


= 54.49 * 0.025 * 0.14 = 0.19 m3

Mass of A387 required


= 0.19 * 8000 = 1520kg

Cost of the A387


= USD$850 * (1520/1000) = USD$1292

Cost of the A387(adjusted by CPI)


= USD$1292 * (210/190) = USD$1428

Cost of the De-entrainment mesh pad, inlet diffuser and liquid level control valve have to be
included as well. Due to the inavailability of their price, a value not more than US$2000 is
assumed in this case for the total cost of these equipment.

Hence a total of USD$(1428+2000) = USD$3428 is approximated for the knockout drum.

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

LITERATURE REVIEW

Developments in Water Gas Shift

Catalysis using Fe-Cr and CuO/ZnO for the HTS and LTS converters has not changed much
for the past 40 years, but continue to be improved marginally. The efforts for improving the
water gas shift reactor performance have been focused on a wide spectrum of subjects. This
involves the modification of the conventionally used catalysts improve overall activity and
stability. In particular, researchers have been making attempts at in developing catalysts
which are more tolerant to sulfur contents.

In comparison with the conventional copper-zinc water-gas-shift catalyst, researchers1 have


reported that noble metal (such as gold, silver, platinum, palladium and rhodium) catalysts
have the advantage of high activity and eliminating the self-heating issue. Langmuir-
Hinshelwood (LH) kinetics have been used to derive the rate equations involving the use of
these newly-developed metal catalysts. A good fit with the experimental data has been
obtained and it is suggested that the LH kinetic model could be a suitable one for application
in catalysis of WGS by other metals. In other papers2, theoretical studies have been
performed to formulate new kinetic expressions for the novel catalysts, with the goal of a
better control over the water-gas-shift’s reaction rate and conversions.

Still, up to now researchers have been trying to optimize the industrial water-gas-shift
reaction by tuning the various parameters involved in the process. Model-based reactor
optimization has been employed for various reactor configurations such as microreactors3,
monolith reactors4 and membrane reactors5 with the objective to achieve an overall reduced
volume for the reactors or a better energy-integration within the system. Furthermore, various
reactor configurations are analyzed in order to find out the limiting values of the main design
variables. In a work by Javier & Co-workers6, it is found that insulating material of the
reactor plays a major role in the shift converters in the sense there exists an optimal thickness
of the insulator that affects the final volume of the reactor as well as other design variables.
Such results from this study will be useful for estimating the minimum and relative sizes that
allows conventional reactor technology.
1 Jian Sun, Joel DesJardins, John Buglass, Ke Liu “Noble metalwater gas shift catalysis: Kinetics study and reactor design
2 M. Levent, Int. J. Hydrogen Energy 26 (2001) 551–558
3. G. Kim, J.R. Mayor, J. Ni, Chem. Eng. J. 110 (2005) 1–10.
4. A.S. Quiney, G. Germani, Y. Schuurman, J. Power Sources 160 (2006)
5. A. Brunetti, Barbieri, E. Drioli, K.-H. Lee, B. Sea, D.-W. Lee, Chem. Eng.Process. 46 (2007) 119–126
6 Javier A. Francesconi, Miguel C. Mussati, Pio A. Aguirre “Analysis of design variables for water-gas-shift reactors

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

Recently a new application for the water gas shift is in the reforming systems for fuel cells.
Fuel cell development has seen remarkable progress in the past decades because of an
increasing need for enhanced energy conversion efficiency and because of serious concerns
about the environmental consequences of using fossil fuels for electricity production.

The water gas shift reaction in fuel cell application has been studied extensively to obtain
highly accurate kinetics expressions in order to create a tool for an integrated and optimized
simulation of a whole fuel processing system. In addition, the new application of hydrogen
gas as a raw material for fuel cells for mobile power sources (PEM fuel cells) requires that
the anode inlet gas have a CO concentration lower than 10-20ppm. Otherwise, the anode is
poisoned and the cell efficiency will drop abruptly. This explains why a water gas shift has to
be employed not just to produce the hydrogen fuel but also to reduce the CO concentration.

In a work by Zalc7, simulation of a fixed bed reactor was carried out, and the water gas shift
reaction forms part of a purification train for a 10kW PEM fuel cell. In that work, a
commercial Cu/Zn/Al2O3 catalyst doped with Ba was used because it showed a higher
activity than the traditional one. A one-dimensional heterogeneous model was applied in that
simulation, and a parametric sensitivity analysis was carried out for some of the process
variables, with the purpose of finding criteria to minimize the reactor volume.

As we can see from the examples above, extensive research has been made into the water gas
shift reaction, with a significant movement towards developing the fuel cell technology. The
water gas shift reaction has played a significant role for the last 60 years at least,
conventionally employed for the production of hydrogen gas for ammonia synthesis. And it
can very well be one of the most important reactions for the 21st century, especially when
fuel cell technology has overtaken all other forms of energy production to claim leader in
fuelling our future. At present, all research made into the water gas shift is definitely a
worthwhile investment.

7 J. Zalc, V. Sokolovskii, D. Loffler, J. Catal. 206 (2002) 169–171

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

CONCLUSION

LTS converter specifications and cost summary


Inlet Composition Outlet Composition
CO 0.0198 0.0034
H2O 0.3399 0.3235
CO2 0.1102 0.1266
H2 0.4955 0.5119
N2 0.0007 0.0007
CH4 0.0320 0.0320
C2H6 0.0020 0.0020

Diameter Height
Dimensions 3.31 4.07

Mass of Catalyst used 34720kg


Inlet Temperature 220 [C]
Outlet Temperature 239.3 [C]
Total Cost USD$229,318

H2 yield at the exit of the LTS : 75.6mol%(Dry Basis)

Knock-out drum specifications and cost summary


Diameter Height
Dimensions 3.31 4.07

Total Cost USD$3,428

In this report, the detailed design of a fixed bed catalytic reactor for the low temperature shift
was presented. Based on the energy and mass balances, the fixed bed catalytic reactor was
modeled in MATLAB. All specifications and costing are presented in the tables above. An
study made on the pressure drop along the bed length shows the exponential relationship of
increasing pressure drop with increasing bed length.

Due to the inavailability of the price data for equipments such as the de-entrainment mesh
pad, inlet diffuser, liquid level control valve and the inert ceramic balls, conservative price
values have been assumed for these equipment and incorporated in the cost mode l of our
design. It is important to take into account the assumptions that have been established for our
modeling. Overall, design and operational optimizations have been completed for this work.

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

BIBLIOGRAPHY

1. Chemical reactor design for process plants / Howard F. Rase


2. Fixed-bed reactor design and diagnostics : gas-phase reactions / Howard F. Rase
3. Handbook of commercial catalysts : heterogeneous catalysts / Howard F. Rase.
4. Perry's chemical engineers' handbook
5. Modelling, simulation, and optimization of industrial fixed bed catalytic reactors
/ S.S.E. H. Elnashaie and S.S. Elshishini.
6. http://en.wikipedia.org/wiki/Souders-Brown_equation

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

APPENDIX A1
Matlab codes
• Calculation of Catalyst Weight and Outlet Compositions

T= input('Please enter initial temperature for reactor in K:');


F= input('Please enter flowrate for reactor in kmol per hour:');
yco= input('Please enter initial mol frac of CO:');
yh2o= input('Please enter initial mol frac of H2O:');
yco2= input('Please enter initial mol frac of CO2:');
yh2= input('Please enter initial mol frac of H2:');
yc2h6= input('Please enter initial mol frac of C2H6:');
ych4= input('Please enter initial mol frac of CH4:');
yn2= input('Please enter initial mol frac of N2:');

Fco= F*yco;
Fh2o= F*yh2o;
Fco2= F*yco2;
Fh2= F*yh2;
Fc2h6= F*yc2h6;
Fch4= F*ych4;
Fn2=F*yn2;

k=exp(12.88-1855.6/T);
K=exp(-4.72+4800/T);
rate=4*k*(yco*yh2o-yco2*yh2/K)/(379*90);

Fco1= Fco -rate*200;


Fh2o1= Fh2o-rate*200;
Fco21= Fco2 + rate*200;
Fh21= Fh2 +rate*200;

cpco= (3.376+(0.557/10^3)*T -(0.031*10^5)*T^(-2))*8.314;


cpc2h6=(1.131+(19.225/10^3)*T-(5.561/10^6)*T^2)*8.314;
cph2o=(3.47+(1.45/10^3)*T +(0.121*10^5)*T^(-2))*8.314;
cpco2=(5.457+(1.045/10^3)*T -(1.157*10^5)*T^(-2))*8.314;
cph2=(3.249+(0.422/10^3)*T +(0.083*10^5)*T^(-2))*8.314;
cpn2=(3.28+(0.593/10^3)*T +(0.04*10^5)*T^(-2))*8.314;
cpch4=(1.702+(9.081/10^3)*T -(2.164/10^6)*T^2)*8.314;

deltaa = 5.457 + 3.249 - 3.376 - 3.470;


deltab = (1.045 + 0.422 - 0.457 - 1.450) * 10^-3;
deltad = (-1.157 + 0.083 - (-0.031) - 0.121) * 10^5;

integral =(deltaa * 298.15 * ((T/298.15) - 1) + (deltab/2)*(298.15^2)*(((T/298.15)^2)-1) +


(deltad/298.15)*(((T/298.15) - 1)/(T/298.15)));

dHco = -41166 + 8.314 * integral;

dT = ((rate * 200) * (-
dHco))/(Fco*cpco+Fh2o*cph2o+Fco2*cpco2+Fh2*cph2+Fc2h6*cpc2h6+Fn2*cpn2+Fch4*cpch4);

T1 = T + dT;

yco1 = Fco1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh2o1= Fh2o1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yco21= Fco21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh21= Fh21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);

ydryco= (yco1/(1-yh2o1));

i=1;

while ydryco>0.005,

k=exp(12.88-1855.6/T);
K=exp(-4.72+4800/T);
rate=4*k*(yco*yh2o-yco2*yh2/K)/(379*90);

k=exp(12.88-1855.6/T1);

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CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report
K=exp(-4.72+4800/T1);
rate1=4*k*(yco1*yh2o1-yco21*yh21/K)/(379*90);

rateavg= (rate+rate1)/2;

Fco = Fco1;
Fh2o = Fh2o1;
Fco2 = Fco21;
Fh2= Fh21;

Fco1= Fco -rateavg*200;


Fh2o1= Fh2o-rateavg*200;
Fco21= Fco2 + rateavg*200;
Fh21= Fh2 +rateavg*200;

cpco= (3.376+(0.557/10^3)*T1 -(0.031*10^5)*T1^(-2))*8.314;


cpc2h6=(1.131+(19.225/10^3)*T1-(5.561/10^6)*T1^2)*8.314;
cph2o=(3.47+(1.45/10^3)*T1 +(0.121*10^5)*T1^(-2))*8.314;
cpco2=(5.457+(1.045/10^3)*T1 -(1.157*10^5)*T1^(-2))*8.314;
cph2=(3.249+(0.422/10^3)*T1 +(0.083*10^5)*T1^(-2))*8.314;
cpn2=(3.28+(0.593/10^3)*T1 +(0.04*10^5)*T1^(-2))*8.314;
cpch4=(1.702+(9.081/10^3)*T1 -(2.164/10^6)*T1^2)*8.314;

integral = (deltaa * 298.15 * ((T1/298.15) - 1) + deltab/2*298.15^2*((T1/298.15)^2-1) +


deltad/298.15*(((T1/298.15) - 1)/(T1/298.15)));

dT = ((rateavg * 200) * (-
dHco))/(Fco*cpco+Fh2o*cph2o+Fco2*cpco2+Fh2*cph2+Fc2h6*cpc2h6+Fn2*cpn2+Fch4*cpch4);

yco = yco1;
yh2o = yh2o1;
yco2 = yco21;
yh2 = yh21;

yco1 = Fco1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh2o1= Fh2o1/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yco21= Fco21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yh21= Fh21/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);

ydryco= yco1/(1-yh2o1);

x(i) = i*200/2.2;
y(i) = T;
a(i) = ydryco;

T = T1;
T1 = T + dT;
i= i + 1;
end

yc2h6 = Fc2h6/(Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
ych4 = Fch4/ (Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
yn2 = Fn2/ (Fco+Fh2o+Fco2+Fh2+Fn2+Fch4+Fc2h6);
Wt=i*200/2.2;

fprintf('mass of catalyst is %f kg.\n',Wt);


fprintf('outlet temperature of LTS is %f K.\n',T1);
fprintf('Outlet CO mole ratio is %f \n',yco1);
fprintf('Outlet H2O mole ratio is %f \n',yh2o1);
fprintf('Outlet CO2 mole ratio is %f \n',yco21);
fprintf('Outlet H2 mole ratio is %f \n',yh21);
fprintf('Outlet C2H6 mole ratio is %f \n',yc2h6);
fprintf('Outlet CH4 mole ratio is %f \n',ych4);
fprintf('Outlet N2 mole ratio is %f \n',yn2);
fprintf('Outlet CO amount is %f \n',Fco1);
fprintf('Outlet H2O amount is %f mol.\n',Fh2o1);
fprintf('Outlet CO2 amount is %f mol.\n',Fco21);
fprintf('Outlet H2 amount is %f mol.\n',Fh21);
fprintf('Outlet C2H6 amount is %f mol.\n',Fc2h6);
fprintf('Outlet CH4 amount is %f mol.\n',Fch4);
fprintf('Outlet N2 amount is %f mol.\n',Fn2);
plot (x,y);
plot (x,a);

Production of Hydrogen via Syngas Route 5-38


CN 4120: Design II
Team 32: Tham Zhi Yong, Andrew (U046754W) LTS Unit Design Report

APPENDIX A2
• Determination of Aspect Ratio
mass = input('Please enter mass of catalyst in lbs:');
flowrate = input('Please enter flowrate in lbs per hour:');
u1 = input('Please enter input viscosity in cp:');
u2 = input('Please enter output viscosity in cp:');
pf = input('Please enter density of feed in lbs per feet3:');
u = (u1+u2)/2;
V = mass/90;

for i=1:600;
hc = i*0.1;
dc = 2*((V/(pi*hc))^0.5);
AR = hc/dc;
area = pi*(dc/2)^2;
G = flowrate/area;
Dp = 0.15/12;
Nre = Dp*G/(2.42*u);
fk = 1.75+150*(0.555)/Nre;
dPft = hc*((fk*G^2/(Dp*pf*32.17*(3600^2)))*0.555/(0.445^3));
dPsi = dPft/(12^2);
dPbar = dPsi/14.7;

x(i,1) = AR;
x(i,2) = dPft;
x(i,3) = dPsi;
x(i,4) = dPbar;
x(i,5) = G;
% if dPsi == 14.7,
% fprintf ('AR = %f.\n',x(i,1))
% end
end
plot(x(:,4),x(:,1));

APPENDIX A3
• Determination of dimensions of catalyst bed and wall thickness
mass = input('Please enter mass of catalyst in lbs:');
AR= input('Please enter AR:');
P = input('Please enter pressure in psi:');
S = input('Please enter maximum allowable stress value in kips per inch square:');

V = mass*144*12/90;
E = 1;
D = (4*V/(pi*AR))^(1/3);
L = D*AR;

t=P*(D/2)/(S*1000*E-0.6*P);

fprintf ('t= %f inches \n',t);


fprintf ('Bulk Volume of catalyst = %f cubic feet \n',V);
fprintf ('Diameter of Catalyst Bed = % f ft \n',D);
fprintf ('Length of Catalyst Bed = %f ft \n',L);

Production of Hydrogen via Syngas Route 5-39


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

Chapter 6 : PRESSURE SWING ABSORPTION

6.1 INTRODUCTION

Conventionally, the industrial purification of hydrogen from steam-methane reforming will


involve the use of a CO2 scrubber with aqueous monoethanolamine (MEA) and a methanator
to convert the unreacted CO to CH4 before recycling it back to the Steam-methane reformer
as feed. However, this purification method gives rise to the problems of personnel safety and
solvent disposal due to the toxicity of MEA [1].

Pressure Swing Adsorption (PSA) has been increasingly adopted as the preferred mode of
purification in the production of oxygen and hydrogen due to the advantages it possessed
over its rivals in terms of selectivity, throughput and efficiency. Compared to the CO2
scrubber (95 - 97% in product purity), the attainable product purity for a typical PSA system
is 99.99% [2]. This can result in a possible improvement in the refinery downstream
operating margin, since a purer treat gas to the hydrotreaters can minimize the effect of
catalyst coking and deactivation, which translates to a lower operating cost. Furthermore,
PSA would have eradicated the problem of solvent disposal since it is a solvent-free process.
However, due to its high operating pressures of up to 20 bar, additional reinforcement of the
process equipments is required which might lead to a higher initial capital cost.

In this report, the PSA configuration is incorporated in the design of a hydrogen plant that is
situated in Singapore. The PSA’s feed is directed from the knockout drum that is downstream
of the low temperature shift reactor (LTS) and the stream composition is approximately in the
range of 75% H2, with the remainder comprising of CO2, CO, CH4 trace amounts of N2 and
H2O.

Production of Hydrogen via Syngas Route 6-1


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.2 PROBLEM STATEMENT

In the interim report that was submitted earlier, a polybed PSA system of 7 – 10 beds was
proposed to recover up to 85% of the hydrogen product at a purity of 99.9%. According to
the Hysys simulation generated for the interim report, table 1 is a summary of the
composition of the incoming stream from the knockout drum to the PSA:

Table 1: Hysys screenshot of the composition of feed entering PSA

Thus the objective of this report is to design a PSA system which is able to achieve a
production of 1.25 x 109 m3 (STP)/yr at a product purity specification of 99.9%.

6.3 THEORETICAL BACKGROUND

6.3.1 Separation via adsorption

Adsorption is a process in which there is a selective transfer of solutes (adsorbates) in the


fluid phase to the surface of solid particles (adsorbents) through the formation chemical
bonds or electrostatic attractions [3]. Figure 1 illustrates the accumulation of adsorbates such
as CO2 on the internal pores surfaces of adsorbents, such as activated carbon for which a
highly porous structure is required to achieve a large surface area for adsorption per unit
volume of adsorbents used.

Production of Hydrogen via Syngas Route 6-2


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

Figure 1: Diagram on adsorption [4]

6.3.2 Pressure-Swing Adsorption (PSA)

A pressure-swing adsorption is a process that selectively separates certain gaseous


components from a gas mixture by effecting a change in the system pressure. The gas
components can be separated either via their molecular characteristics or affinity for an
adsorbent material. Under high pressure, the adsorbates are selectively adsorbed onto the
adsorbents, which is the crux of the whole separation process. The system pressure is
subsequently lowered so as to effect the desorption of the adsorbates, thereby allowing the
regeneration of the bed.

6.3.3 Skarstrom Cycle

The design of this report’s PSA system is based on the basic form of Skarstrom Cycle [5]
which comprises of 2 beds and 4 basic steps:

• Pressurization

o Pressurization of the PSA unit increases the affinity of the adsorbate with the
absorbent bed which causes enrichment of the less selectively adsorbed species.
This is done using the feed.

Production of Hydrogen via Syngas Route 6-3


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

• High Pressure Adsorption

o The raffinate is recovered during this process until the absorbent bed is relatively
saturated.

• Blow-down

o Depressurization of the PSA unit occurs at this step, which allows the adsorbed
species to desorb from the bed and be removed.

• Purge

o The bed is purged with part of the raffinate from the HPA step of another bed.
This is to regenerate the bed and allow it to be used for another cycle.

6.3.4 Adsorbents

Figure 2: Picture of activated carbon

Activated carbon, is a general term that includes carbon material derived mostly from
charcoal. Possessing an exceptionally high surface area due to a high degree of microporosity,
it is used in the PSA process for the adsorption of CO2 and CH4.

Production of Hydrogen via Syngas Route 6-4


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

Zeolites are hydrated aluminosilicate minerals commonly referred to as "molecular sieves".


The term molecular sieve refers to a particular property of these materials with the ability to
selectively sort molecules based primarily on a size exclusion process. This is due to a very
regular pore structure of molecular dimensions. Zeolites are considered crystalline while
activated carbon is amorphous. Zelites are used in PSA design to remove N2 and CO from the
effluent gas.

6.4 DESIGN CONSIDERATIONS

Being a dynamic process, the model for PSA involves the evaluation of nonlinear partial
differential equations. The high level coupling of the model parameters further adds to the
complexity of the whole simulation process. Thus before the commencement of the
simulation process, an appropriate model should be selected and certain assumptions would
have to be adopted so as to reduce the modeling complexity.

The assumptions made were as follows [5]:

1. An isothermal system is assumed.

2. There is negligible frictional pressure drop along the bed length.

3. Mass transfer between the gas and the adsorbed phases is accounted for all the steps
and is sufficiently represented by the Linear Driving Force (LDF) model. During the
adsorption and the purge steps, the total pressure in the bed remains constant while it
varies exponentially with time during the blow-down and pressurization.

4. Fluid velocity in the bed varies along the length of the column, as determined by the
overall mass balance.

5. The flow pattern is described by the axial dispersed plug flow model.

6. Equilibrium relationships for the components are represented by extended Langmuir


isotherms.

7. The ideal gas law applies.

8. The PSA process is assumed to be equilibrium controlled.

Production of Hydrogen via Syngas Route 6-5


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

In the LDF model, the mass transfer rate equation was represented as:

∂qi
∂t
= k i q i* − q i ( )
ε p D p  c0 
ki = Ω 
2
 i = A ( or ) B
rp  q0 i
D
where Dp = M ,
τ
Ω LDF parameter ( = 15 )
where D molecular diffusivit y(chapman − Enskog Equation)
M

τ tortuosity ( = 3)
c0 gas concentrat ion in feed gas
q0 solid phase concentrat ion in equilibriu m with c o

In order to simplify the model, the mass transfer coefficient, ki for macropore control was
adopted by assuming that the adsorbents were spherical in shape with no micropore diffusion
of the adsorbates.

By neglecting the interactions between the adsorbed components and assuming that the
reduction of the vacant surface area for the adsorption of A is solely due to the adsorption of
the other components, the extended Langmuir model was applied as follows:

K i (q i )m p i
qi =
1+ ∑ K jpj
j

where (qi )m is the maximum amount of adsorption of species i for coverage of the entire
surface.

Production of Hydrogen via Syngas Route 6-6


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.5 ACTUAL MODELING OF PSA

Even after simplifying the LDF model, a moderate degree of difficulty still exist in the
simulation of PSA via the use of COMSOL. Coupled with the issue of time constraint, the
complexity of the model was further reduced to as follows:

1. All the water was assumed to be removed via the use of a layer of silica gel before the
gas stream entered the PSA.

2. The subsequent six component system was reduced to a binary system of hydrogen
(carrier gas) and carbon dioxide (adsorbate).

3. The molecular diffusivity of carbon dioxide in hydrogen, DM was derived using


Hirschfelder Equation for which the molecules were assumed to be non-polar and
non-reacting.

4. The pure component isotherms and the respective constants on a common adsorbent
were applied.

5. The Peclet number was assumed to be a constant due to its small numerical value.

6. The product of time constants, a1 and a2 and time, t for both pressurization and blow-
down step were assumed to be 6.

The selection of hydrogen and carbon dioxide as the two components was in accordance with
the Hysys simulation whereby they accounted for more than 93% of the total number of
moles entering PSA (CO2 ≈ 19%, H2 ≈ 75%). Thus for conservative design, the mole ratio of
H2 to CO2 was assumed to be 1:3. Activated carbon [7] was employed as the adsorbent in this
simulation due to its higher affinity for CO2 as compared to H2.

Production of Hydrogen via Syngas Route 6-7


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

The following partial differential equations were employed:

6.5.1 Component Mass Balance

For which A = CO2 and B = H2,

∂ 2 cA ∂c ∂v ∂c 1− ε ∂qA
− DL 2 + v A + cA + A + =0
∂z ∂z ∂z ∂t ε ∂t

6.5.2 Overall Mass Balance

∂2C ∂C ∂v ∂C 1− ε ∂qA ∂qB


− DL 2 + v + C + + ( + ) =0
∂z ∂z ∂z ∂t ε ∂t ∂t

6.5.3 Pressure terms

∂P
= ( PH − PL )( a1 ) e − a1t ( For Pressuriza tion step )
∂t
∂P
= − ( PH − PL )( a 2 ) e − a 2t ( For Blow - down step )
∂t
∂P
=0 ( For Adsorption and Purging steps )
∂t

6.5.4 Adsorption rates

∂qB e ∂qA
= kB (qB − qB ) e
= kA (qA − qA )
∂t ∂t

Production of Hydrogen via Syngas Route 6-8


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

The above equations were subsequently converted to dimensionless form so as to firstly,


reduce the number of variables and complexity in the modeling and secondly, to facilitate in
the subsequent scale-up to the actual plant capacity.

6.5.5 Overall Mass Balance in Dimensionless Form


∂v ε Rg T0 ∂xA ∂xB ∂P 1
= −qSA ( + γs )−
∂χ 1− ε P ∂τ ∂τ ∂τ P

6.5.6 Component Mass Balance in Dimensionless Form


∂yA 1 ∂2 yA ∂yA 1− ε RgT0  ∂x ∂x 
= − v + qSA (yA −1) A + γs yA B  = 0
∂τ Pe ∂χ 2
∂χ ε P  ∂τ ∂τ 

6.5.7 Dimensionless Pressure terms



∂ P  PL  a1 L  −a1 Vo
= 1 −  e
∂τ  PH  v  (For Pressurization step)
 o 

∂ P  PL  a2 L  −a2 Vo
= −1 −  e
∂τ  PH  v  (For Blow-down step)
 o 

∂P
= 0 (For Adsorption and Purging steps)
∂τ

6.5.8 Dimensionless Langmuir Adsorption Isotherms

 yA PPH   yB PPH 
 bA   bB

∂x A  Rg To  ∂xB  R T
g o 
= αA  − xA  = αA  − xB 
∂τ 1+ b yA PPH + b (1− yA )PPH 
∂τ 1+ b yA PPH + b (1− yA )PPH 
 A
Rg To
B
Rg To   A
RgTo
B
RgTo 
   

Production of Hydrogen via Syngas Route 6-9


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

The 5 dimensionless equations were inputted into COMSOL for simulation with the set of
boundary conditions.

6.5.9 Boundary Conditions

Pressurization Adsorption


1 dy A
Pe dχ
χ =0 = v χ =0 (y A χ =0 −
− yA χ =0+ ) −
1 dy A
χ=0 = v χ =0 (y A χ=0−
− y A χ =0+ )
Pe d χ
dy A dy A
χ =1 = 0 χ =1 = 0
dχ dχ
v χ =1 =0 v χ =0 =1

Blowdown Purge

dy A dy A
χ = 0 = 0 χ =0 = 0
d χ dχ
dy A
d χ
χ =1 = 0 −
1 dy A
Pe dχ
χ =1 = v χ =1 (y A χ =1+
− y A χ =1− )
v χ =1 = 0 v χ =1 = purge to feed velocity ratio (G )

Production of Hydrogen via Syngas Route 6-10


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.6 MODEL OPTIMIZATION

The aim of the optimization process is to maximize the recovery of the H2 product whilst
attaining the specified purity of 99.9%. For a reasonable and simplified design of the PSA
system, the following heuristics would be adhered to in this report [8]:

• A two bed system was assumed for the COMSOL-Matlab simulation.

• Bed Porosity should be maintained in the range of 0.3 – 0.5.

• Adsorption time should be close to the breakthrough time.

• Adsorption and Desorption time should be kept constant for 2 bed processes.

• Purge to feed volume ratio, G should in the range of 1.0-2.0.

• The ratio of pressurization time to adsorption time should be capped at 0.2.

• The superficial velocity entering the bed should not exceed 75% of the minimum
fluidizing velocity [5].

There are multiple decision parameters that govern the operations of PSA and this includes
the bed length, bed diameter, superficial velocity of the feed and purge ratio, G. A systematic
approach was thus adopted wherein a variation of one of the parameters would be performed
with the others held constant. For this varied variable, the optimum point would be that at
which the required purity of 99.9% was achieved with the maximum allowable recovery. By
maintaining the constant value for this variable, this optimization process was subsequently
repeated for all the other parameters.

Production of Hydrogen via Syngas Route 6-11


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.6.1. Process Methodology

In this report, the following optimization sequence was adopted:

1. Initial approximation of the adsorption time from the breakthrough curve.

2. Determination of the cyclic steady state.

3. Refinement of the pressurization time.

4. Optimization of feed superficial velocity and diameter of the bed.

Production of Hydrogen via Syngas Route 6-12


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.6.2 Initial approximation of the adsorption time from the breakthrough curve

According to A. Varnia [9], an industry expert, a 5-bed PSA system with the height and
diameter of approximately 8.5 m and 3.2 m respectively, can achieve a hydrogen production
of (STP) 1.25 x109 m3/yr at 99.9% product purity. From this capacity and diameter, an inlet
flow-rate of 3.33 m3/s and subsequently, a velocity of 0.41m/s, were approximated with the
Hysys simulation. Thus this initial bed height, diameter and velocity were adopted in
COMSOL to estimate the time period for breakthrough to occur (the time duration before
which the maximum allowable adsorbate concentration (CO2) in the effluent gas (H2) is
exceeded). The purge to feed volume ratio, G was also assumed to be at 2 [8].

Breakthrough
occur at T =
17 τ

Figure 3: Breakthrough curve of yco2 with time

Based on this initial breakthrough time, an adsorption time could be subsequently


approximated to initiate the optimization process, since the duration of the high pressure
adsorption should be theoretically equal to that in order for breakthrough to occur [8].

Production of Hydrogen via Syngas Route 6-13


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

From the COMSOL simulation for the adsorption step, it could be observed that the time
duration for breakthrough was about 17 τ in dimensionless time and this translates to:

T * BL
t=
Vo
17 * 8.5
=
0.4 / 0.36
= 130 s

Thus according to figure 7.1, 130 s was the upper limit for the varying of the subsequent
adsorption times. The purity of the product started to decline once the breakthrough time was
exceeded and in order to attain a high level of product purity, it is necessary to set the
adsorption time to as near as possible to the breakthrough time.

6.6.3 Determination of Cyclic steady state

The dynamic steps in PSA meant that no steady state would be attained. However, after a
sufficiently large number of cycles, there will be a point in time whereby the profiles
achieved by the bed at the end of a cycle will be the same at the start of the next and that is
when cyclic steady state is achieved.

In order to determine the cyclic steady state, the number of cycles, h required for each run of
simulation was varied as shown below in figure 3. Four values of h (3, 4, 10 and 14) were
used. For each run of simulation, a plot of the yco2 wave front versus bed length was
generated and subsequently, they were compared on the same graph. There was a shift in the
wave front to the right with an increase in the number of cycles. However, beyond the run for
10 cycles, a constant wave front was observed, which led to the conclusion that 10 cycles was
required for cyclic steady state to be attained.

Production of Hydrogen via Syngas Route 6-14


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

Run for 10 and 14 cycles


Run for 3 cycles

Run for 5 cycles

Figure 4: Plot of varying yco2 wave front versus bed length

6.6.4 Refinement of the pressurization time

The durations of the adsorption and pressurization time are two important parameters that
affect the performances of a PSA system. According to the simulations performed by S. Jain
[8], the ratio of the pressurization time and adsorption time should be capped at a limit of 0.2
so as to achieve the best possible result for both purity and recovery. According to the earlier
discussion, the optimum adsorption time should be set near to the breakthrough time and a
value of 120 s was assumed for conservative reasons in order not to exceed the breakthrough
time. The pressuration time was subsequently varied to obtain the best result. As seen from
figure 7.3, the change in pressurization time was inversely proportional to recovery.

(amount of H 2 obtained during adsorption −


amount of H 2 used in purge step)
Re cov ery =
(amount of H 2 used during adsorption step in feed +
amount of H 2 fed during pressurization step)

Production of Hydrogen via Syngas Route 6-15


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

According to the above equation used in the calculation of recovery, with an increase in the
pressurization time, more of the H2 will be fed during the pressurization step and this will
result in a decrease in recovery, which was consistent with the trend displayed in figure 7.3.
The values of Tads = 120 s and Tpr = 24 s were selected for further optimization.

Purity vs Re cove ry for varying Tpr at cons tant Tads =


120s
0.9992

0.999

0.9988

0.9986
Tads = 120 s
0.9984
Tpr = 24 s Tads = 120 s
0.9982
Tpr = 22 s
0.998

0.9978

0.9976
0.817 0.819 0.821 0.823 0.825 0.827 0.829 0.831

Figure 5: Plot of purity versus recovery at varying Tpr (Tads = 120 s)

6.6.5 Possible optimization of feed superficial velocity and diameter of the bed

If the purity specification of 99.9% was not attained or if there was potential for further
improvement in product recovery, the last parameter for optimization would be the feed
superficial velocity. In this section, the feed velocity was adjusted while maintaining a
constant Tads and Tpr. An optimum value of 0.4 m/s for feed superficial velocity was
subsequently attained from figure 7.4. It should be noted that the calculated feed superficial
velocity should not exceed 75% of the minimum fluidizing velocity. This was because
fluidization of the fixed bed could result in the possible loss of adsorbents with the exiting
product stream. The minimum fluidizing velocity was calculated to check for the validity of
D p vs ρ f (0.003)(0.4)(9.634)
the superficial feed velocity: Re = = = 1619
(1 − ε ) µ (1 − 0.36)(1.116 x10 −5 )

Production of Hydrogen via Syngas Route 6-16


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

Turbulent flow occurs where 500<Re<200000

To calculate Vf, the modified Ergun equation for turbulent flow [10] was used:
1
 3( ρ s − ρ ) gd p 2 1
(3)(850 − 9.634)(9.81)0.003 2
u t =   = ( ) = 2.78
 ρ  (9.634)

Particle Density, ρp = 850 kg/m3 Fluid Density, ρf = 9.634 kg/m3

g = 9.81 m/s2 Particle Diameter, dp = 0.003 m

ε = 0.36 Kinematic Viscosity, µ = 1.180 x 10-5 Pa s

Based on the above mentioned heuristics, the calculated feed superficial velocity of 0.4 m/s
was safely within the range of less than 75% of the minimum fluidizing velocity, which was
calculated to be 2.8 m/s.

Constant Tads , Tpr (120 s, 22 s), varying V

1.00000

0.99950

0.99900
Purity

0.99850

0.99800 V = 0.41 m/s


V = 0.40 m/s
0.99750

0.99700
0.80000 0.81000 0.82000 0.83000 0.84000
Re cove ry

Figure 6: Plot of purity versus recovery for different feed superficial velocity

Production of Hydrogen via Syngas Route 6-17


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.7 FINAL RESULTS AND DISCUSSIONS

Adsorption Time, Tads = 120 s

Pressurization Time, Tpr = 24 s

Superficial feed velocity, V = 0.4 m/s

Recovery = 82.0%

Purity = 99.9%

Total output − Total purge


Pr oductivity = = 1.15 x 109 m3 (STP)/yr
Total time

where total time is time taken for both pressurization and high pressure adsorption to occur

Required capacity = 1.25 x 109 m3 (STP)/yr

It can be observed that the productivity achieved in this simulation was lower than the
required plant capacity. One probable reason could have been due to the higher recovery
assumed in the Hysys interim report (85%), which had subsequently resulted in a lower
quantity of feed required.

It should also noted that the separation performed in this report is on a binary system, which
fails to account for the presence of the other components, such as CO, CH4 and N2 that are
present in the actual feed stream to PSA. Thus the actual purity might have in fact been lower.

Production of Hydrogen via Syngas Route 6-18


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.8 COST ESTIMATIONS

The cost estimation is done by assuming a diameter of 3.0 m and bed length of 8.5 m.

D2
Volume of vessel, V = π L
4

32
=π (8.5)
4
= 60 m 3

From Figure A.7, purchased cost of vessel using carbon steel,

C po = 850 × 60 = $ 51,000

Production of Hydrogen via Syngas Route 6-19


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

( P + 1) D
+ 0.00315
2[850 − 0.6( P + 1)]
Pressure factor, FP ,vessel = for t vessel > 0.0063m pp925 [1]
0.0063

Where P = pressure in barg and D = diameter of vessel

P = 25 bar = 24 barg

(24 + 1)3
+ 0.00315
2[850 − 0.6(24 + 1)]
FP ,vessel = = 7.63
0.0063

Purchased cost of vessel after pressure correction and adjusted for inflation

CEPCI in Nov 2007


C p = C op × Fp, vessel ×
CEPCI in Sept 2001

CEPCI in Nov 2007 = 593.6 [Chemical Engineering February 2008] (latest data available)

593.6
C p = $51,000 × 7.63 × = $ 581,833
397

Assuming auxiliary equipment, which include expander, control valves and safety valves
piping,

Total Cp = $ 581,833 × 1.3 = $ 756,383

Production of Hydrogen via Syngas Route 6-20


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

Calculation of cost of activated carbon

Mass of activated carbon used = V(1- ε b) ε p

= 60 × (1-0.36) × 850

= 32,640 kg

Cost of Calgon activated carbon ≈ $5/kg [2]

Cost of activated carbon = 32,640 × 5 = $ 163,200

The real PSA bed for H2 purification is packed by not only activated carbon, but also Zeolite
which is of much higher price than activated carbon.

Total cost for a PSA adsorber = $ 581,833 + $ 163,200

= $ 745,033

This estimated cost is expected to be less than the actual price because the actual PSA bed
will use not only activated carbon but also Zeolite

For 2-PSA adsorber = $ 745,033 × 2

= $ 1,490,066

Assuming installation of PSA is 10% of total cost

Therefore, total estimated cost of installed 2 PSA bed system

= $ 1,490,066 × 1.1

= $ 1,639,073

Production of Hydrogen via Syngas Route 6-21


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.9 CONCLUSION

For this report, varying degrees of success has been achieved in the simulation of the PSA
system. A productivity of 1.15 x 109 (STP) m3/yr at 99.9% product purity and 82% recovery
has been obtained from the COMSOL Matlab simulation of a two bed, binary PSA system
through the variation of pressurization time, Tpr and feed superficial velocity, V. However,
this productivity still falls short of the required capacity of the H2 plant which was fixed at
1.25 x 109 (STP) m3/yr. A reasonable explanation for this shortfall could have been attributed
to the lower feed required arising from a higher product recovery assumed initially (85%).

Industrially, the attainable recovery is within 80 – 90% at a purity of up to 99.999% with a 7 -


10 bed configuration and the use of more steps such as pressure equalization, co-current
pressurization to increase the recovery of the system. Thus it might not have been feasible to
achieve a recovery of 85% at a purity of 99.9% with a complete multi-component simulation
of a two bed system.

Due to severe time constraints, only the binary system was considered in this simulation and
this could have been expanded further into a multi-component system if more time was
allowed. Furthermore, the simulation was performed for one adsorbent (activated carbon),
which is not applicable for a multi-component system where at least two adsorbents are
required for the near complete sorption of the various components so as to achieve a product
with a very high level of purity.

Finally, a buffer tank could have been considered in the overall design of the system, so as to
deal with the possible occurences of irregular flow from the upstream units. Through the
installation of a buffer tank, irregular flow rates can be eliminated and this will ensure the
smooth operation of the PSA system. Furthermore, in times of an upstream unit upset, the
avaliability of the buffer tank can continue to sustain the PSA operations until the upstream
unit is up and running again.

Production of Hydrogen via Syngas Route 6-22


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.10 NOTATIONS

Symbol Meaning Symbol Meaning

c Concentration v Superficial Velocity

q Adsorbed Phase Vo Interstitial Velocity


Concentration
(mol/kg)

K Mass transfer L Bed Length (m)


coefficient

DL Molecular D Bed Diameter (m)


Diffusivity

Pe Peclet Number qas Saturated Adsorbed


phase concentration
(CO2)

T Time (s) qbs Saturated Adsorbed


phase concentration
(H2)

T Temperature (K) b Langmuir constant

Ε Void Fraction Y Gas phase


concentration

z Axial position in G Purge to feed ratio


adsorption bed (m)

Vf Minimum g Gravitational
fluidization velocity acceleration (m/s2)

Dp Particle Diameter µ Dynamic Viscosity


(Ns/m)

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CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

Subscripts

Symbol Meaning Symbol Meaning

A CO2 s Saturated

B H2 H, L High, low

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CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.11 APPENDIX

The molecular diffisivity:

Assuming 1) negligible viscosity change over temperature 2) Feed at 50ºC

A: Carbon Dioxide B: Hydrogen

Using Equation 24 -33 [6],

1/ 2
 1 1 
0.001858T 3/ 2
+ 
 MA MB 
D AB =
Pσ AB
2
ΩD

σ A +σB
Where σ AB =
2

ε AB = ε Aε B

κ = 1.38 x10 −16 ergs / K

From Appendix K, Table K.2

εA
= 190
κ σ A = 3.996
εB σ B = 2.968
= 33.3
κ

Ω D = 0.88216(int erpolate)

D AB = 3.645E-2 cm2/s = 3.645E-6 m2/s

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CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

The original axial dispersed plug flow model [] is given by

∂ 2ci ∂c ∂v ∂c i 1 − ε ∂ q i
− DL + v i + ci + + =0 where
∂z 2
∂z ∂z ∂t ε ∂t

∂ 2 ci
− DL = axial dispersion term
∂z 2

D L = 0.7 D M + 0.5vd p = 0.7 D M + rp v

∂ci ∂v
v + ci = convective mass transfer term
∂z ∂z

∂ci
= accumulation term
∂t

1 − ε ∂q i
= adsorption to solid phase term
ε ∂t

for i = A and B, A = carbon dioxide and B = hydrogen

∂ 2c A ∂c ∂v ∂c A 1 − ε ∂ q A
− DL + v A + cA + + =0
∂z 2
∂z ∂z ∂t ε ∂t

We will first derive the overall mass balance equation which will be used to find the velocity
profile along the bed.

The OVERALL MASS BALANCE, which is the sum of component mass balances

∂2 ∂ ∂v ∂ (c A + c B ) 1 − ε ∂ q A ∂ q B
− DL ( c A + c B ) + v (c A + c B ) + (c A + c B ) + + ( + )=0
∂z 2
∂z ∂z ∂t ε ∂t ∂t
cA + cB = C

∂ 2C ∂C ∂v ∂C 1 − ε ∂ q A ∂ q B
− DL +v +C + + ( + )=0
∂z 2
∂z ∂z ∂t ε ∂t ∂t

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CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

The total concentration is not a function of the distance of bed

c A + c B = C ≠ f (z ) and

∂ 2 C ∂C
= =0
∂z 2 ∂z

The overall material balance becomes

∂v ∂C 1 − ε ∂ q A ∂ q B
C + + ( + )=0
∂z ∂t ε ∂t ∂t

∂v 1  ∂C 1 − ε  ∂ q A ∂ q B  
=−  + +
∂z C  ∂t ε  ∂t ∂t  

P
C=
R g T0

∂C 1 ∂P
=
∂t R g T0 ∂t

∂v R g T0 1 − ε ∂ q A ∂ q B ∂P 1
=− ( + )− OVERALL MASS BALANCE
∂z P ε ∂t ∂t ∂t P

This overall mass balance equation is used to find the velocity profile along the bed

Dimensionless form

∂v ε R g T0 ∂ x A ∂x B ∂P 1
= −q SA ( + γs )− D’LESS OVERALL MASS BALANCE
∂χ 1− ε P ∂τ ∂τ ∂τ P

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CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

We will then proceed to find component mass balance

∂ 2c A ∂c ∂v ∂c A 1 − ε ∂ q A
− DL + v A + cA + + =0
∂z 2
∂z ∂z ∂t ε ∂t

yAP
cA =
RT

∂ 2 yA P ∂y P y P ∂v ∂y A P 1 − ε ∂ q A
− DL +v A + A + + =0
∂z RT
2
∂z RT RT ∂z ∂t RT ε ∂t

∂ 2 yA ∂y ∂v ∂y A 1 − ε RT ∂q A
− DL + v A + yA + + =0
∂z 2
∂z ∂z ∂t ε P ∂t

Substitute OVERALL MASS BALANCE INTO COMPONENT MASS BALANCE

∂v R g T0 1 − ε ∂ q A ∂q B ∂P 1
=− ( + )−
∂z P ε ∂t ∂t ∂t P

∂ 2 yA ∂y  R g T0 1 − ε ∂ q A ∂ q B ∂P 1  ∂y A 1 − ε RT ∂ q A
− DL + v A + y A  − ( + )−  + ∂t + ε P ∂t = 0
∂z 2
∂z  P ε ∂ t ∂ t ∂t P 

Simplify the above equation

∂ 2 yA ∂y A  R g T0 1 − ε ∂ q A ∂ q B  1 − ε RT ∂ q A
− DL + v + y − ( + )  + =0
∂z 2 ∂z
A  P ε ∂ t ∂ t ε P ∂t
 

Rearrange it

∂y A ∂ 2 yA ∂y 1 − ε R g T0  ∂q ∂q 
= DL −v A +  ( y A − 1) A + y A B  = 0 COMP. MASS BAL
∂t ∂z 2
∂z ε P  ∂t ∂t 

∂y A 1 ∂2 yA ∂y 1 − ε R g T0  ∂x ∂x 
= − v A + q SA  ( y A − 1) A + γ s y A B  = 0
∂τ Pe ∂χ 2
∂χ ε P  ∂τ ∂τ 

D’LESS COMPONENT MASS BALANCE

Production of Hydrogen via Syngas Route 6-28


CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.12 CONSTANTS APPLIED IN COMSOL SIMULATION

Temperature 323K

Bed voidage 0.36

Particle density 0.85 g/m3

qco2 7.12 mol/kg Saturated adsorbed CO2

qH2 4.32 mol/kg Saturated adsorbed H2 [7]


bco2 2.54e-6 Pa-1 CO2 Langmuir constant

bh2 7.02e-8 Pa-1 H2 Langmuir constant

kco2 0.1 s-1 Mass transfer coeff CO2

kh2 1.0 s-1 Mass transfer coeff H2

High P 2.5e6 Pa

Low P 1e5 Pa

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CN 4120: Design II
Team 32: Zhang Zihong (U046816H) PSA Unit Design Report

6.13 REFERENCES

[1] Retrieved from ‘www.astrochemicals.com/10136.htm’, 24/03/2008

[2] Tinall, B.M and Crews, M.A, ‘Economics of export steam for hydrogen plants,’
Hydrogen Engineering, (2003) 39

[3] J D Seader and E J Henley, “Separation Process Prinicples”, John Wiley & Sons, pp 798
(1998)

[4] Retrieved from ‘http://www.norit-americas.com/images/adsorption-image.gif’

[5] ‘Pressure Swing Adsorption’, D.M. Ruthven et al, VCH Publishers, 1994, Pg 225

[6] J.R Welty, C.E.Wicks, R.E. Wilson, G.Rorrer, Fundamentals of Momentum, Heat, and
Mass Transfer, John Wiley & Sons, Inc. (2001) 4th ed

[7] J.H Park, J.N Kim, S.H Cho, Performance Analysis of Four-Bed H2 PSA Process Using
Layered Beds, AIChE Journal (2000) Vol 46

[8] S.Jain, A.S.Moharir, P.Li, G.Wozny, Heuristic Design of pressure swing adsorption: A
preliminary study, Separation and Purification Technology 22 (2003) 25-43.

[9] V.Aspi (2008) Singapore Refinery Company, Jurong Island, Singapore, Personal
communication

[10] Retrieved from


‘http://faculty.washington.edu/finlayso/Fluidized_Bed/FBR_Fluid_Mech/fluid_bed_scroll.ht
mcosting’

[11] Turton et al, Analysis, Synthesis, and Design of Chemical Processes, 2nd edition,
Prentice Hall, 2007

[12] Retrieved from


‘http://www.apswater.com/shopdisplayproducts.asp?id=157&cat=Activated+Carbon’

Production of Hydrogen via Syngas Route 6-30


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Chapter 7 : HEAT EXCHANGER NETWORK


EXECUTIVE SUMMARY
Energy integration is of utmost importance in a chemical plant, where huge demands are being
placed on plant personnel to fully utilize available utilities, in order to obtain the most
economical and practical solution. To achieve optimal heat integration, it would involve the
systematic development of a heat exchange network (HEN), together with detailed designs of
each and every heat exchanger.

The primary targets set out in this problem statement would be:
 To design a heat exchanger network for a hydrogen plant to be sited in Singapore
 To look into possible optimization of the heat exchanger network, considering a
multitude of network variations and possible network evolution
 To design one of the heat exchangers in detail after the heat exchanger network has been
finalized

Pinch analysis was the method of choice in deriving a minimum energy recovery (MER) network.
Though 2 loops were identified, various infeasibilities limited the evolution of the MER network.
The final network was eventually chosen based on the minimum total annual cost. The total
annual cost of the selected network was within 1% of the target set.

Detailed thermal sizing of the SMR feed preheater was then performed. A TEMA style AES
shell and tube exchanger was utilized for this service. Computation of the estimated area, heat
transfer coefficient, pressure drops and cost were calculated. The final design for the heat
exchanger is projected to be able to handle about 99% of its intended heat load.

ACKNOWLEDGEMENTS
This section dedicates acknowledgements to all who have helped the author by offering their
valuable insights and advices. In particular, the author would like to express gratitude to Prof.
Rangaiah for his advice. Last but not least, this work would not have been possibly done without
the coordination and teamwork in Team 32 (CN4120 – Sem 2 of AY2007/08), hence the author
would like to thank all of them for their assistance and understanding.

Production of Hydrogen via Syngas Route 7-1


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.1 DESIGN METHODOLOGY OF A HEAT EXCHANGER NETWORK


Pinch technology was systematically adopted for the design and evolution of this design problem.
Substantial effort was first channeled into the collection of relevant stream data. Manual
determination and verification of these stream data properties, coupled with cost optimization
were then carried out before the actual synthesis of the heat exchanger network. Two software
programs, Hysys and HX-Net, were extensively used in this design process to facilitate data
extraction, data processing, pinch analysis and super-targeting.

7.1.1 Determination & Verification of Stream Data Properties Extracted from Hysys
Stream data properties (mass flow rates, M, supply temperature, Ts, target temperature, Tt, heat
capacity, Cp and convective heat transfer coefficient, h) extracted into HX-Net from Hysys have
to be validated first before the actual design of the heat exchanger network can proceed. Data
relevant to the design are validated using suitable equations and correlations.

7.1.1.1 Calculations of Maximum Design Velocities


As HX-Net uses a default stream velocity of 1 m/s, which would not be an accurate reflection of
the actual stream velocities, it is essential to compute manually the maximum allowable design
velocities. Correlations detailing these calculations are shown belowError! Bookmark not defined..
• Allowable velocity for given liquid =
1
 2
( Allowable velocity for water ) Density of water 
 Density of given liquid 
where the allowable velocity of water in low carbon steel tubes is taken to be 10 ft/s.
Therefore, a sample calculation for HP steam generation is shown below:
1
 62.4 lb/ft 3  2
Allowable velocity = 10 ft / s  3
= 11.2 ft / s = 3.43 m / s
 49.4 lb/ft 
• For gases and dry vapors in steel tubes,
 1800 
Allowable velocity for gas (ft/s) =  
 ( Absolute pressure in psia )(Molecular weight ) 
A sample calculation for Natural Gas feed stream is shown below:
 1800 
Allowable velocity for NG feed =   = 18.42 ft / s = 5.62 m / s
 (580.2 psia )(16.45) 

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

The computed values for each process and utility stream were tabulated as follows in Table 1 and
Table 2. It can be seen that the liquid stream velocities were in the range of 1 to 4 m/s and vapor
streams were also well within the stipulated standard process design guidelines. Hence, we can
deduce that reasonable estimates have been obtained and these values were subsequently used in
place of the default value in HX-Net.

Table 1: Maximum design velocities for vapor streams.


Absolute Allowable Allowable Guideline
Vapor Molecular Pressure
Pressure Velocity Velocity VelocitiesError!
Streams Weight Category Bookmark not defined.
(psia) (ft/s) (m/s)
NG Feed 580.2 16.45 18.42 5.62 High
SMR Feed 394.6 17.63 21.58 6.58 High
SMR Outlet 381.5 12.67 25.89 7.89 High Atmospheric
HTS Outlet 363.5 13.12 26.06 7.94 High pressure:
LTS Outlet 360.5 13.12 26.17 7.98 High 10 to 30 m/s
Combustible
14.5 28.91 87.92 26.8 Atm High pressure:
Air
5 to 10 m/s
Flue Gas 11.5 27.07 102.02 31.1 Atm

Table 2: Maximum design velocities for liquid streams.


Allowable Guideline
Density Allowable
Liquid Streams Velocity VelocitiesError!
(lb/ft3) Velocity (m/s) Bookmark not defined.
(ft/s)
HP Steam Generation 49.4 11.2 3.43
1 to 4 m/s
Cooling Water 62.4 10.0 3.05

7.1.1.2 Determination of Flow Area Diameter

The flow area diameter in HX-Net was defaulted as 0.0254 m or equivalent to 1 inch. According
to heuristics1, 3 4 in. (19 mm) is a recommended trial diameter to commence design calculations.
Selection of a suitable tube thickness also depends on internal pressure and corrosion issues. For
plain carbon steels where severe corrosion is not expected, a minimum allowance of 2.0 mm
should be used.Error! Bookmark not defined. Hence a tube thickness of 14 BWG (wall thickness = 2.11
mm) was used. Therefore, considering the above factors, an internal flow area diameter of
0.01483 m was adopted for HX-Net computations.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.1.1.3 Calculations of Convective Heat Transfer Coefficients (HTC)

Of paramount importance is the verification of extracted HTC values against manually calculated
values computed from suitable correlations. This is because the magnitude of HTC values of
each component stream are used to compute the overall heat transfer coefficient, U, which is
then used to calculate the heat transfer area, an essential component of overall costing. Therefore,
it is essential to ensure the accuracy of the HTC values in order to obtain an accurate cost
estimation of the heat exchangers.

Heat transfer that occurs in a heat exchanger is classified under forced convection in a closed
conduit. For this type of flow, several correlations are applicable, dependent on whether the flow
is laminar or turbulent. After computing the Reynolds number for all the streams using the
maximum allowable velocity calculated in the previous section, it was found that the flow was
mostly in the turbulent region. For single phase turbulent flow either in gases or liquids, the
correlation proposed by Dittus and Boelter in 1930 can be readily applied2:
k
hi = 0.023Re 0.8 Pr n
d
where n = 0.30 if fluid is being cooled, and n = 0.40 if fluids is being heated.

To obtain the necessary dimensionless numbers in the above correlation, the arithmetic-mean
bulk temperature is used as the basis for evaluating stream properties. However, for the heat
exchanger involved in steam generation in the convection section of the furnace, there arises a
need to compute the convective HTC value for a 2-phase flow system where in-tube boiling
occurs. The Boyko-Kruzhilin equation3 was utilized to compute the HTC value as shown below
as it is generally conservative and adequately accurate for most purposes. Sample calculation for
steam generation in convection section of furnace:

kl  (ϑ ϑm )i + (ϑ ϑm )o 
hi = 0.024 Re i0,.l8 Pri0,l.43  
di  2 

 ϑ − ϑv   ϑ − ϑv 
where (ϑ ϑm )i = 1 +  l  xi , (ϑ ϑm )o = 1 +  l  xo
 ϑv   ϑv 

Production of Hydrogen via Syngas Route 7-4


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

kl = thermal conductivity of the fluids, W/m °C; d i = inner diameter of tube, m

ϑl = density of liquid phase, kg/m3, ϑv = density of vapor phase, kg/m3


xo = inlet vapor fraction, xi = outlet vapor fraction

1.0 + 2.2 
hi = 0.024
0.58
( )(
240407 0.8 0.94 0.43  )  = 29474 W/m 2 .°C
0.01483  2 
It was also noted that the heat exchanger cooling the LTS Outlet stream would result in the
condensation of that process stream into a 2-phase system too. The Boyko-Kruzhilin equation
was similarly applied to obtain its HTC value.

For the flue gas stream in the convection section, initial estimates of its Reynolds number seem
to indicate that the fluid is in transition flow. In this case, the HTC value would be bounded by
the laminar and turbulent conditions. Firstly, the HTC assuming a laminar flow regime was
calculated using the Hausen correlationError! Bookmark not defined.:

0.0668 Re Pr (d i L )  µ
0.14
k f  
hi = 3.65 + 23
 
d i  1 + 0.04 + [Re Pr (d i L )]  µ w 

where hi is the mean coefficient for the entire length L of a single tube, which was designated to
be 16 ft (4.88 m) long according to heuristicsError! Bookmark not defined. available in literature.
 µ  ki  0.0668 Re Pr (d i L ) 
Neglecting the viscosity correction term  i ,
 hi = 3.65 + 23
 µ w,i  di  1 + 0.04 + [Re Pr (d i L )] 

Another HTC value was then calculated as if the flow was turbulent using the Dittus-Boetler
correlation. The final estimated HTC value for transition flow would then be calculated as
 Re − 2000 
follows: (hi )T [
= hi + hi − hi  ] 
 8000 

7.1.1.4 Fouling Factors


When process and service fluids flow through a heat exchanger, fouling will usually occur, the
extent dependent on the nature of the fluid. The deposited material on the heat transfer surfaces
will normally have a low thermal conductivity and this will decrease the overall heat coefficient.
Hence the effect of fouling should be incorporated into the preliminary design, so as to oversize

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

the exchanger to allow for a performance reduction in actual operations. The list of fouling
factors used is included in the following
Table 3.

Table 3: Typical fouling factors for process and utility streams.


Typical Fouling Factors Typical Fouling Factors
Type of Stream
(ft2.h.°F./Btu) (m2.°C/W)
Natural Gas 0.001 0.000176
Light Hydrocarbon Vapors (clean) 0.001 0.000176
Hydrogen (saturated with H2O) 0.002 0.000352
Flue Gas 0.001-0.003. 0.002 was used 0.000352
Air (atmosphere) 0.0005-0.001. 0.00075 was used 0.000132
Steam (non-oil bearing) 0.0005 0.0000881
Cooling Water (treated makeup) 0.001 0.000176

7.2 TARGETING

Besides achieving an integrated heat exchanger network which satisfies the heating and cooling
requirements of the various process streams, an important consideration is always an economic
one; the network design should be one that is a balance between cost and efficiency. Different
scenarios would warrant different approaches towards network synthesis. If utility costs are high,
a network which maximizes energy recovery within the plant would then be the optimal choice.
Conversely, if fuel costs are low, it would be an appropriate approach to opt for a network with
fewer heat exchangers so as to lower annual costs. Hence, an estimation of capital (purchased
equipment) cost and operating (utility) costs would have to be factored into the total annual cost
of the network, and subsequently, it would provide the direction and set the criteria for
evaluating each possible network design.

7.2.1 Cost Considerations

The total annual cost (TAC) of a network is calculated from the following formula:
TAC = OC + AF × CC
where OC is the operating cost corresponding to the total utilities cost, AF is the annualization
factor and CC is the capital cost. The annualization factor is given by:

Production of Hydrogen via Syngas Route 7-6


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

 Rate of return(% ) 
1 + 
AF =  
100
Plant life

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

The rate of return is 10% as stated in the problem statement. However, although the plant life
was stated to be 15 years, a plant life of 6 years was used instead after consultation with
Professor Rangaiah. This is due to the typical of the lifespan of heat exchangers. These values
were then keyed into HX-Net, where it will be used to automatically estimate the TAC with
appropriate OC and CC inputs.

7.2.2 Utility Cost Calculations


As the cost data given by the problem statement were in units incompatible with the input format
in HX-Net, there was a need to convert them to suitable units. Using high pressure (HP) steam
for sample calculations,
Cost of saturated HP steam (42 bar) = US$33 / metric ton = US$0.033 / kg
Temperature of Saturated HP Steam (42 bar) = 254.3°C
Mass heat of vaporization = 1726 kJ/kg
Plant operation time = 8000 h/year = 28800000 s/year
Cost index of HP Steam

=
(Cost ofHP steam )(Plant operation time ) (US $ 0.033 kg )(28800000 s yr )
=
mass heat of vaporization 1726 kJ kg

= US $550.6 kW . yr

Similarly, the cost of cooling water used was calculated as follows:


Cost of cooling water = US$0.067 / m3
Temperature range of cooling water = 90 to 120 °F = 32.22 to 48.89 °C
At 32.22 °C, Mass heat capacity = 4.314 kJ/kg °C, Mass density = 1002 kg/m3
At 48.89 °C, Mass heat capacity = 4.320 kJ/kg °C, Mass density = 989.1 kg/m3
Taking the arithmetic mean,
Mass heat capacity = 4.317 kJ/kg °C, Mass density = 995.55 kg/m3
Cost index of cooling water

=
(Cost of cooling water )(Plant operation time )
(Mass density )(mass heat capacity )(Temperature difference )

=
(US $0.067 m )(28800000 s yr )
3

(995.55 kg m )(4.317 kJ kg − C )(48.89 C − 32.22 C ) = US $26.9 kW . yr


3 o o o

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.2.3 Heat Exchanger Capital Cost Estimations


Capital cost estimations have to be inputted into HX-Net so as to facilitate cost target
calculations. The capital cost index is represented in HX-Net as: CC = a + bA c
where CC = capital cost and a, b and c are constants.
Based on 1986 costs, the capital cost coefficients were given as a = 30800, b = 750 and c =
0.81.4 Any cost data must take into account the effect of time on purchased equipment cost, and
this was carried out by using the Chemical Engineering Plant Cost Index (CEPCI) to incorporate
inflationary effects over time5.
CEPCI for 1986Error! Bookmark not defined. = 318, CEPCI for Nov 20076 = 526
Therefore, correcting for changing economic conditions over time:
 526 
CC =  (
 30800 + 750 A
0.81
)
= 50946 + 1241A 0.81
 318 

7.2.4 Supertargeting
Generally, as the minimum approach temperature, ∆Tmin, increases, a dual effect is seen. Firstly,
the amount of heat recovered from hot process streams decreases, leading to an increased need
for utilities, thus raising associated operating costs. However, having an increased ∆Tmin would
also mean more effective heat transfer, as the temperature gradient, acting as the driving force,
would be greater. Therefore, a smaller heat transfer area for the same target load would be
achieved, giving cost savings in terms of reduced capital investment in smaller heat exchangers.

Figure 1: (Left) Total cost and operating cost as a function of ∆Tmin.


Figure 2: (Right) TAC and OC as a function of ∆Tmin.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Supertargeting using the cost indices that were computed earlier (capital and operating costs)
was carried out. It allows us to select the optimal ∆Tmin corresponding to the minimum TAC for a
network. As seen from Figure 1, the optimal ∆Tmin is in the region of 4°C. However, this was on
the low side and could be attributed to the faster rate at which the operating cost is increasing as
compared to the savings in the capital cost as ∆Tmin increases. Hence, to provide a sufficient
driving force, a ∆Tmin value of 10°C was chosen instead, since this would conform more to
industrial standards and also lead to only a marginal increase of TAC (less than 1%).

7.2.5 Comparison between the usage of HP and LP Steam Generation


It was found that TAC was actually a negative quantity, indicating that the designed network was
generating profits instead, due to the sale of high-value HP steam. Hence, it was decided that a
choice should be made to either generate HP or LP steam. After making the necessary
computations and keying the updated LP steam properties into HX-Net, a range target graph was
generated, as seen from Figure 2. It can be seen that the TAC has dropped significantly as
compared to Figure 1 where HP steam was used. Furthermore, ∆Tmin decreased to an even lower
value. Hence, it was decided that the usage of HP steam would be a better economical choice.

7.2.6 Calculation of Utility Targets


Once the heating and cooling requirements of the process streams have been determined together
with a specified ∆Tmin, the minimum amount of utilities can then be estimated. The temperature-
interval analysis, also known as the problem table algorithm, can be used for such a purpose.Error!
Bookmark not defined.
Alternatively, the composite curve method first proposed by Umeda et al.7, can

be applied.

Figure 3: (Left) Hot and cold composite curves.

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Utility
Pinch
CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 4: (Right) Utility composite curve showing the utility pinch created by HP steam generation.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

As seen from
Figure 3, the graph is reminiscent of a threshold problem which only requires a cold utility,
unaffected by ∆Tmin. Figure 4 shows the utility composite curve where HP steam generation
and cooling water were used as the cold utilities. It is evident that the usage of HP steam
generation actually introduces a utility pinch at around 253.3 to 254.3°C, the temperature of
saturated HP steam at 42 bar. Hence the initial threshold problem with no pinch has now evolved
into one with a utility pinch, where pinch analysis can be applied by treating the utility streams
as “dummy” process streams8.

Figure 5: Network targets for ∆Tmin = 10°C.

7.3 MER NETWORK DESIGN

Although there are no process pinches in this design problem, a utility pinch has been introduced
with the usage of HP steam generation. A method, first introduced by Linnhoff and Hindmarsh9,
would be used to design two networks of heat exchangers, one on the hot side (above pinch) and
one on the cold side of the pinch (below pinch). Certain rules would have to be followed
according to the abovementioned method1:
1. The heat exchanger network is designed from the most constrained point where the approach
temperature difference is at its minimum, i.e. at ∆Tmin.
2. At the pinch, streams are paired such that above the pinch, Cp, cold ≥ Cp, hot and below the
pinch, Cp, hot ≥ Cp, cold.
3. The heat duty of each interior heat exchanger is selected to be as large as possible, so as to
reduce the total number of exchangers.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

4. Hot utilities are added up to meet the heating energy targets, and no cold utilities are used
above pinch.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

5. Cold utilities are added up to meet the cooling energy targets, and no hot utilities are used
above pinch.
The conditions for feasible pinch matches are as follows:
 Number of streams going out of pinch ≥ Number of streams going into pinch. This is to
ensure that there are adequate streams for stream matching as certain utilities are not
permitted above and below the pinch.
 MCp of the out streams ≥ MCp of the in stream. This is to ensure no minimum driving
force violations.

7.3.1 Stream matching above pinch


The number criterion is fulfilled here as there are 2 out streams (including the HP steam
generation utility) and 2 in streams. Although the only process cold stream (SMR Feed, circled
red in Figure 6) above the pinch should have been matched with the Flue Gas stream according
to the MCp criterion, this match was purposely left out as it was decided that the all the heat
energy above the pinch should be used for HP steam generation in the convection section. This
would not only give rise to more profits obtained from exporting the HP steam credit, but also,
the steam generation tubes in the convection section can act as shield tubes in the first few rows
of the convection section. This is because these tubes are exposed directly to radiation from the
radiant section. During actual furnace operations, there will be fluctuations in the temperature of
the flue gas; hence these tubes can thus act as a heat sink to regulate the temperature of the
exiting flue gas.

Excluding the above exception, the rest of the streams were matched so long as the head loads
were comparable and no driving force violations exist. MCp criterion need not may obeyed in
this non-pinch matches.

The pinch point has been calculated by HX-Net to be 263.3 / 253.3°C.

7.3.2 Stream matching below pinch


The number criterion is also fulfilled here with 2 out streams versus 1 in stream. A pinch match
was made between the HTS outlet stream and the SMR feed stream (circled yellow in Figure 6),

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

following the MCp criterion. Similar to the above pinch scenario, the rest of the matches were
then matched accordingly using similar heat loads and no driving force violations as the basis.
Stream splitting was only carried out for the HP steam generation stream. However, it was
represented in this way, rather than as separate utility streams, for network simplicity and easy
summing up of the total cooling load needed above the pinch.

7.3.3 Number of units in MER network


After stream matching has been completed for both sides of the pinch, the total number of heat
exchangers in the MER network was compared with the calculated minimum number of units
using the following equation:
u min = n p + nu − 1
where n p represents the number of process streams and nu the number of utilities.

Minimum number of units above utility pinch = 4 + 1 − 1 = 4


Minimum number of units below utility pinch = 6 + 1 − 1 = 6
Total number of heat exchangers in the HEN network = 6 + 4 = 10
Therefore, MER condition has been met in the designed heat exchanger network as seen from
Figure 6.

7.3.4 Alternative MER Network Designs for Consideration


Two other MER networks were also designed to see if alternative MER networks would give a
lower TAC.

7.3.4.1 Network 1a
As seen from Figure 7, the heat exchanger network above the pinch remained the same. However,
a variation below the pinch was adopted. The combustible air to the furnace was solely preheated
by the convection section, instead of being heated by the LTS outlet stream, HTS outlet stream
and the convection section. This was because of considerations over the physical limitations to
the placement of the heat exchangers as increased pipe lengths and insulation would then have to
be factored into the cost of the network. However, it can be seen from the network performance
and cost indices table in Figure 7 that this network would not offer a lower TAC. Instead, capital
cost and total area would be higher than that of the original network design (Network 1). Since it
cannot be ascertained at this preliminary design stage that piping cost would be a major factor in

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

TAC and the units that make up a hydrogen plant are usually located close by, it has been
advised that Network 1 would suffice at this juncture.

7.3.4.2 Network 1b
As seen from Figure 8, again the heat exchanger network above the pinch remained in a similar
configuration as the previous 2 networks discussed. The combustible air was now preheated
solely by the LTS outlet stream. The TAC and total area calculated by HX-Net seemed to
indicate that this network was at a similar performance level as that of Network 1.
However it was apparent that cooling water would have to be used to cool the hot flue gases,
which would not be feasible as the primary use of the convection section should be to heat up the
other process cold streams. Cooling water should only be used as a last resort unless stack gas
temperatures are above environmental regulations. Hence this alternative was also discarded.
The network performance and cost indices of each MER network are summarized in Table 4.
The total areas for the 3 networks were satisfactorily within 20% of the target area. Network 1 is
thus selected for network evolution.

Table 4: Network performance and cost indices of each MER network.


Network 1 Network 1a Network 1b
% of % of % of
HEN HEN HEN
Target Target Target
Capital (US$) 7.540e+6 114.1 7.717e+6 116.8 7.533e+6 114.0
Total Cost
-4.819e+7 100.6 -4.813e+7 100.7 -4.819e+7 100.6
(US$)
Total Area (m2) 1.774e+4 82.67 1.836e+4 85.56 1.769e+4 82.41

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 6: Network 1, original MER network design

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 7: Network 1a, air preheated solely by furnace convection section

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 8: Network 1b, air preheated solely by LTS outlet stream

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.4 NETWORK EVOLUTION

Evolution of the selected MER network (Network 1) was carried out, so as to reduce the
number of heat exchangers required, which would then result in a lowering of capital
costs. However, it is to be noted that the operating costs of the network would then
increase consequently as some energy recovery would have to be sacrificed and more
utilities would be needed. As a result, the TAC of an evolved network may be lower than
the MER network. Hence evolution of the MER network was done to facilitate a
comparison of the TAC of both networks.

7.4.1 Steps involved in network evolution


 Determination of the scope of improvement.
 Identification of loops present in exchanger network. An even number of units in
a loop have to be ensured
 Breaking of loop, calculate resultant stream temperatures and check driving forces
 Restore ∆Tmin if there is any violation by forcing heat along the path
 Continue breaking other loops and restoring ∆Tmin one at a time if possible and
attractive
The number of minimum units assuming no pinch is u min = n p + nu − 1 = 7 + 2 − 1 = 8 ,

which was found to be the same as the minimum number of units computed by HX-Net.
Hence the scope of improvement would be 10 − 8 = 2 loops. These 2 loops were
identified by HX-Net and shown respectively in Figure 9 and Figure 11.

7.4.2 Evolution of 1st loop


The heat exchanger with the smallest heat load (circled green) was identified and its heat
load transferred to the next heat exchanger in the loop, as indicated by the green arrow in
Figure 9. The smallest heat load was eliminated because the cost savings in removing a
small exchanger would be much higher than the cost incurred in increasing the area of
another larger exchanger already in place. The temperatures of the affected streams were
then re-calculated with the new heat loads placed on them.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

The evolved loop is shown in Figure 10. It can clearly be seen that there are now 2 heat
exchangers which have a temperature cross situation (circled white). Efforts were made
to restore ∆Tmin, however as there were no cold utilities already in place at the ends of the
2 process hot streams below the pinch, there was no viable way to prevent ∆Tmin from
being violated and a temperature cross situation to ensue. It would not be a good solution
to have to add a cooling water as a cold utility at the ends of either of the 2 streams, as it
defeats the purpose of evolving a network and reducing the number of exchangers. Hence
this loop was not considered for evolution.

7.4.3 Evolution of 2nd loop

Similarly, the heat exchanger with the smallest heat load (circled magenta) was identified
and its heat load transferred to the next heat exchanger in the loop, as indicated by the
magenta arrow in Figure 11. Again, as seen in Figure 12, a temperature cross was
encountered in one of the heat exchangers (circled white) due to the lack of cold utility
below the pinch, at the other end of the process stream. Hence, similar reasons prevented
the restoration of ∆Tmin, hence this loop was also not considered for evolution.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 9: Network 1 showing 1st loop.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 10: Evolution of 1st loop.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 11: Network 1 showing 2nd loop

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Figure 12: Evolution of 2nd loop.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.5 HEAT EXCHANGER DESIGN


Shell and tube exchangers are the most commonly used type of heat transfer equipment in
the process industry, as they offer a large range of operating conditions, good mechanical
layout, large surface area in a compact setup, flexibility in choice of construction
materials, ease of fabrication and cleaning, and most importantly, well-established design
procedures. Standards of the American Tubular Heat Exchanger Manufacturers
Association (TEMA) are universally adapted. For petroleum and related industries with
generally severe duties, heat exchangers are typically fabricated in accordance with class
“R” TEMA specifications.10

7.5.1 Stream Data


With reference to Figure 6, the heat exchanger chosen for thermal sizing would be the
one using the SMR outlet stream to preheat the SMR feed stream (circled yellow). The
details of the unit are shown below:

Table 5: Heat exchanger stream properties.


Hot Stream Inlet Outlet
Temperature 851.9 606
Effective Cp in kJ/kg°C 2.964
Thermal Conductivity, kf, in W/m°C 0.183
Density, ρ, in kg/m3 4.031
Viscosity, µ, in cP 0.02797
Mass flow rate, M, in kg/hr 183500
Fouling Factor in hr.sq. ft.°F /BTU 11 0.002
Fouling Factor in m°C/W 0.000352

Cold Stream Inlet Outlet


Temperature 253.3 539.4
Effective Cp in kJ/kg°C 2.483
Thermal Conductivity, kf, in W/m°C 0.067
Density, ρ, in kg/m3 9.258
Viscosity, µ, in cP 0.02002
Mass flow rate, M, in kg/hr 183500
Fouling Factor in hr.sq. ft.°F /BTU Error! Bookmark
not defined.
0.001
Fouling Factor in m°C/W 0.000176

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.5.2 Material of Construction

The choice of a suitable material of construction is more often that not determined by
corrosion-related issues. Factors which influence the amount of corrosion include
oxidizing agents, solution pH, temperature, fluid velocity, films etc.12 For the heat
exchanger chosen for further thermal design, both the hot and cold streams are not of a
corrosive nature as hydrogen levels still has not made up a significant proportion of the
streams, and are also of low enough temperature such that temperature-related corrosion
is negligible. Even if fluid velocities are high, it can be overcome with design features
such as tube inserts or impingement baffles within the exchanger unit. After considering
the above factors, it was decided that carbon steel, the most common material for heat
exchangers, would be a suitable material for both the tube and shell sides.

7.5.3 Shell and Tube-Side Fluid Allocation


The following are considerations for fluid allocation in a heat exchanger with no phase
change10:
Table 6. Analysis for shell and tube-side fluid allocation
Factor General Guidelines SMR Outlet / SMR Feed
Corrosion More corrosive fluid to tube-side to Both are non-corrosive
reduce cost of expensive alloy or
clad components
Fouling More fouling fluid to tube-side to SMR outlet stream is more
increase fluid velocity, reduce fouling due to the presence
fouling and facilitate cleaning of H2
Fluid Temperatures Hotter fluid to tube-side to reduce SMR outlet stream is hotter
heat loss, cost and for safety than SMR inlet
reasons
Operating Pressures Higher pressure stream to tube-side Both streams are of similar
to reduce material cost pressures
Pressure Drop Fluid with lower allowable Both streams have similar
pressure drop to tube-side to obtain allowable pressure drops
higher heat-transfer coefficients
Viscosity More viscous fluid to shell-side, SMR outlet stream slightly
provided turbulent flow is achieved more viscous, but difference
not significant
Stream Flow Rates Fluid with lower flow rate to shell- Both streams have similar
side flow rates

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

From Table 6, it was decided that the SMR outlet stream would be assigned to the tube-
side, while the SMR feed stream would be the shell-side fluid.

7.5.4 Exchanger Type


Designation of TEMA shell and tube heat exchangers follows a three-letter code to
specify the front end stationary head type, shell type and rear end head type. It was
decided that the AES type exchanger would be employed. Front head type A has a
removable channel and cover plate and is the least expensive option. Shell type E is the
most common shell construction but higher pressure drop may ensue. This can be
controlled by varying the tube layout and baffle pitch. Rear end head type S is most
commonly used for internal floating head designs, and allows for the cheapest straight
tube removal bundle.

7.5.5 Baffles
Baffles are used in the directing of fluid stream across the tubes so as to increase the fluid
velocity and thus improve the rate of transfer. For single segmental baffles, the maximal
baffle cut is about 45%. Optimum baffle cuts range from 20 to 25%, while the optimum
spacing is usually 0.3 to 0.5 times the shell diameter.10

7.5.6 Tube Dimensions


Typical tube diameters range from 5 8 in. (16 mm) to 2 in. (50 mm). A smaller diameter
( 5 8 to 1 in.) is usually used for most duties, as they give smaller and cheaper exchangers.
According to heuristics13, 3 4 in. (19 mm) is a recommended trial diameter to commence
design calculations. However, considering the large volume of cooling water needed, a 1
in. tube diameter (do = 25.4 mm, di = 21.18 mm) was employed.

Selection of a suitable tube thickness depends on internal pressure and corrosion issues.
For plain carbon steels where severe corrosion is not expected, a minimum allowance of
2.0 mm should be used.12 Hence a tube thickness of 14 BWG (wall thickness = 2.11 mm)
was used. Tube length L was designated to be 16 ft (4.88 m) long according to heuristics4
available in literature.

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CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.5.7 Tube Arrangements


Several tube arrangements exist: equilateral triangular, square or rotated square pattern.
An equilateral triangular pattern, as seen in Figure 13, was used as recommended by
heuristics, as it provides higher heat transfer rates. Furthermore, heavy fouling requiring
mechanical cleaning is not expected in this particular heat exchanger since shell-side
fluid is relatively clean. A tube pitch Pt (distance between tube centres) of 1.25do was
also utilized in accordance with common practices10.

Figure 13. Equilateral triangular tube arrangement.

7.5.8 Calculations
The log mean temperature difference ∆Tlm is calculated as follows:

∆Tlm =
(T
1 )
− t2 − (T2 − t1 ) (851.9 − 539.4 ) − (606.0 − 253.3)
= = 332.2oC
ln
(T1 − t2 ) ln
(851.9 − 539.4)
(T2 − t1 ) (606.0 − 253.3)
where ∆Tlm = log mean temperature difference
T1 = hot fluid temperature, inlet
T2 = hot fluid temperature, outlet
t1 = cold fluid temperature, inlet
t2 = cold fluid temperature, outlet
To account for non-ideal counter-current flow within the exchanger, a correction factor Ft
is applied. The correction factor is a function of shell and tube fluid temperatures, and the
number of shell and tube passes, and is correlated as follows:
T1 − T2 851.9 − 606.0 t2 − t1 539.4 − 253.3
R= = = 0.859 S= = = 0.478
t2 − t1 539.4 − 253.3 T1 − t1 859.9 − 253.3
From the temperature correction factor plots for one shell pass, two or more tube passes10
or using a correction factor equation derived by Kern, the corresponding Ft = 0.883.

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Since this value is above the benchmark value of 0.75 for an economic exchanger design,
it confirms that the single pass configuration is sufficient. The true temperature difference
∆Tm can then be computed:

∆Tm = Ft ∆Tlm = 0.883 × 332.2 = 293.3o C


Since both hot and cold streams are gases, the overall heat transfer coefficient U should
be 10-50 W/m2°C. A value of 10 W/m2°C was used as the starting value for iteration.

The provisional required heat transfer area A would then be:


Q 36158.9 kW × 1000
A= = = 12300 m 2
U∆Tm 10 W / m 2 ° C × 293.3° C
Tubes with the following properties are chosen for use:
do = 25.4 mm
di = 21.18 mm
L = 4.88 m
As a first approximation, an allowance of 50 mm for tube-sheet thickness (2 tubes sheets)
was included, take L = 4.83 m .

External surface area of one tube, At = πd o L = π (25.4 × 10 −3 )(4.83) = 0.385 m 2

A 12300
Number of tubes needed, N t = = = 31948 ≈ 31900
At 0.385
Number of tubes per pass, assuming 2 passes, Np = 31900 ÷ 2 = 15950
π
Tube internal cross-sectional area, Ai =
4
(21.18 × 10 )
−3 2
= 0.0003523 m 2

Area per pass = N p × Ai = 15950 × 0.0003523 m 2 = 5.62 m 2

mass flow rate per hr 1


Volumetric flow = ×
3600 density
183500 kg / h 1
= × = 12.65 m 3 / s
3600 s 4.031 kg / m 3

volumetric flow 12.65 m 3 / s


Tube-side velocity, u t = = = 2.25 m / s
area per pass 5.62 m 2

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Check the tube-side velocity to ascertain reasonable value. The velocity is a bit too low
for high pressure vapor streams, where velocities should range from 5 to 10 m/s10. This
will be checked on later together with the pressure drop specifications.

7.5.8.1 Tube-Side Heat Transfer Coefficient Calculations


ρu d 4.031 × 2.25 × 0.02118
Reynolds number, Re = t i = = 6870
µ 0.02797 × 10 −3
C p µ 2.964 × 10 3 × 0.02797 × 10 −3
Prandtl number, Pr = = = 0.453
kf 0.183
L 4.83 × 10 3 mm
= = 228
di 21.18 mm
From Figure 12.23, the tube side heat transfer factor, j h = 4.1 × 10 −3 .

Tube side heat transfer coefficient then can be computed by 10:


−0.14
 µ  kf 
hi = j h Re Pr 0.33
   
 µw   di 
 µ 
Neglecting the viscosity correction factor   due to non-viscous nature of gases,
 µw 
 0.183 
hi = 4.1 × 10 −3 × 6870 × 0.4530.33 ×  2°
 = 187 W / m C
 0 . 02118 

7.5.8.2 Shell-Side Heat Transfer Coefficient Calculations


For two tube passes in triangular pitch, the tube bundle diameter Db is estimated based on
the following empirical equation10:
1 1
N  n1
 31900  2.207
Db = d o  t  = 25.4  = 5237 mm = 5.235 m
 K1   0.249 
Since a split-ring floating head was used, the bundle diametrical clearance is
approximated as 78 mm10. Therefore, minimum shell inside diameter Ds = Db + 78 mm =
5315 mm = 5.315 m. This could be too large a value and would be corrected in the next
iteration by increasing the number of tube passes.

Kern’s “bulk-flow” method was used to estimate the shell-side heat transfer coefficient
and pressure drop. Although Kern’s method does not take into consideration the bypass

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Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

and leakage streams unlike the more vigorous Bell’s method, it was still adopted as it is
simple to apply and provides a satisfactory preliminary approximation.
An initial baffle spacing, lB equal to 0.4Ds, and a baffle cut of 25 percent was used to give
a balance of good heat transfer rates and minimal pressure drop.
Baffle spacing, l B = 0.4 × 5315 = 2126 mm = 2.126 m
tube pitch, pt = 1.25 × 25.4 = 31.75 mm = 0.03175 m
( pt − d o )Ds l B (31.75 − 25.4) × 5237 × 2126 × 10 −6
Cross-flow area, As = = = 2.23 m 2
pt 31.75

Ws (183500 kg / h × 1 h / 3600 s )
Mass velocity, G s = = = 22.9 kg / s m 2
As 2.23

Gs 22.9 kg / s m 2
Linear fluid velocity, u s = = = 2.47 m / s
ρ 9.258 kg / m 3
The shell-side fluid velocity is lower than the recommended 5-10 m/s and would be taken
note in the next iteration.

Shell-side equivalent diameter, de (hydraulic diameter) for an equilateral triangular pitch


arrangement is computed as follows:

de =
d0
(
1.10 2
pt − 0.917 d o2 = ) 1.10
25.4 mm
[
31.75 2 − 0.917(25.4 mm ) = 18.0 mm = 0.018 m
2
]
Gs d e 22.9 × 18.0 × 10 −3
Re = = = 20600
µ 0.02002 × 10 −3
Cpµ 2.483 × 10 3 × 0.02002 × 10 −3
Pr = = = 0.74
kf 0.067
0.14
 µ 
Shell-side Nusselt number, Nu = j H Re Pr  13

 µw 
where jH is the dimensionless heat transfer factor.

For the calculated Reynolds number, the corresponding value of jH is 0.0042. 10


 µ 
Neglecting the viscosity correction term   ,
µ
 w

Production of Hydrogen via Syngas Route 7-32


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Nu = j H Re Pr 1 / 3 = 0.0042 × 20600 × 0.741 / 3 = 78.3


Nu × k f 78.3 × 0.067 W / m 2 ° C
hs = = = 291 W / m 2 ° C
de 0.0180 m

7.5.8.3 Overall Heat Transfer Coefficient Calculations


The overall heat transfer coefficient is given by
d 
d o ln 0 
1
=
1
+
1
+  di  + do × 1 + d0 × 1
U h0 hod 2k w d i hid d i hi
Where U = overall heat transfer coefficient, W/m2°C
ho = outside fluid film coefficient, W/m2°C
hi = inside fluid film coefficient, W/m2°C
hod = outside dirt coefficient (fouling factor), W/m2°C
hid = inside dirt coefficient, W/m2°C
kw = thermal conductivity of the tube wall material, W/m2°C
From literature, thermal conductivity of carbon steel = 55 W/m2°C 10
 0.0254 
0.0254 ln 
1
=
1
+
1
+  0.02118  0.0254
+ ×
1
+
0.0254
×
1
U 291 5679 2 × 55 0.02118 2839 0.02118 187
o
U = 95.3 W / m 2 C
95.3 − 10
% error from estimated U = × 100% = 853%
10
Since the overall heat transfer coefficient is not within 30% deviation from the initial
estimate, the design is not satisfactory and the calculated U would be used as the initial
value for the next iteration.10

7.5.8.4 Tube-Side Pressure Drop Calculations


Tube-side pressure drop is computed as:
 L  µ 
−m
 ρu 2
∆Pt = N p 8 j f    + 2.5 t
  di  µ w   2

Where jf is the dimensionless friction factor.

Production of Hydrogen via Syngas Route 7-33


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

Ignoring the viscosity correction term,


4.031 × 2.25 2
∆Pt = 2[8 × 0.0052(228) + 2.5] = 245 N / m 2
2
The calculated tube side pressure drop is below the specifications (below 3 psi =
20.68kPa, the designated pressure drop for heat exchangers with vapor service). The
number of tube passes should be increased in the next round of iteration.

7.5.8.5 Shell-Side Pressure Drop Calculations


Shell-side pressure drop is computed as:
−0.14
D  L  ρu s2  µ 
∆Pt = 8 j f  s    
 de  l B  2  µw 
Ignoring the viscosity correction term,
 5315 mm  4.83 m  9.258 × 2.47 2
∆Pt = 8 × 0.045   = 6820 N / m 2
 18 mm  2.126 m  2
Both pressure drops for the tube side and shell side are too low. The calculations would
have to be iterated again.

7.5.9 Modification of Design


As the overall heat transfer coefficient is not within 30% deviation from the initial
estimate, some modifications of the design parameters need to be implemented.

Firstly, 5 more iterations were done using the same overall parameters, each time using
the new calculated value of U. This generated a U that was within 30% of the previous
value. However, the value is 515.1 W/m2°C, still way much higher than the
recommended range of 10-50 W/m2°C. Furthermore, the shell side pressure drop was
more than the specifications.

Therefore, it was decided that a thicker tube with tube diameter (do = 50.8 mm, di = 46.59
mm) should be used. This yielded better results. After another 3 iterations, the value of U
decreased to 351 W/m2°C, however, the tube side and shell side velocities remained
above the 5-10 m/s guideline. A final change to the baffle cut from 25% to 45% was used.

Production of Hydrogen via Syngas Route 7-34


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

After 2 iterations, it resulted in the following design specifications, which met most of the
specifications and remained fairly constant after a few iterations.
Table 7: Final heat exchanger specification.
Tube Side Shell Side
Fluid velocity (m/s) 32.6 (5-10 m/s) 26.7 (5-10 m/s)
h (W/m2°C) 1650 576.3

∆P (kPa) 19.2 ( 20.68<∆P<258) 150 ( 20.68<∆P<258)


Overall
2
A(m ) 351
U (W/m2°C) 351
Q (MW) 36.1 (99.9% of target heat load)

This was taken to be the final heat exchanger specification as shown in Table 7.

7.5.10 Exchanger Cost


The cost of the single heat exchanger that was designed was estimated using the
CAPCOST program5. The bare module cost of a heat exchanger is computed as follows:
C BM = C p ° FBM = C p (B1 + B2 FM FP )
°

log10 C p ° = K 1 + K 2 log10 A + K 3 (log10 A)


2

log10 F p = C1 + C 2 log10 P + C 3 (log10 P )


2

Where Cp° = purchased cost, FM = material factor (carbon steel = 1), FP = pressure factor,
A = heat exchanger area (m2), P = design pressure (barg), B1, B2, K1, K2, K3, C1, C2, and
C3 are constants.

For a 1-2 shell and tube exchanger, made up of carbon steel tubes and shell, with a heat
exchanger area = 351 m2 and a maximum design pressure of 30 barg (an estimated 10%
safety factor was added on top of the normal operating pressure of 27 bar) , the bare
module cost as computed by CAPCOST is:
log10 C p ° = 4.8306 − 0.8509 log10 (351) + 0.3187[log10 (351)]
2

C p ° = US $ 53,644
log10 F p = −0.00164 − 0.00627 log10 (30) + 0.0123[log10 (30)]
2

F p = 1.04

Production of Hydrogen via Syngas Route 7-35


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

C BM = C p ° FBM = 53644(1.63 + 1.66 × 1 × 1) = US $ 176,488

Given that CEPCI in 3Q 2001 = 39755 and CEPCI for Nov 20076 = 526, correcting for
inflation over year, taking into consideration that the above equations apply to the cost in
3rd quarter 2001,
 526 
C BM =  US $ 176,488 = US $ 233,835 ≈ US $ 234,000
 397 

7.6 RECENT DEVELOPMENTS

In recent years, there has been a growing interest in the research on the aspect of heat
exchanger fouling, with emphasis being placed on the methods of prevention and
cleaning. This is due to the high costs and time incurred with such operations. In order to
account for the effects of fouling in heat transfer, numerous models and simulations have
been developed to predict the rate of fouling but their accuracies are often limited by the
use of ideal fouling resistance that has few uses in real world applications. Several
measures have been adopted to combat fouling, an especially prevalent problem in
refineries as refineries seek to increase their profit margins, increasingly buying and
processing heavier, high sulphur and cheaper crudes, leading to elevated deposition
problems.

Strategies to ease problems includes13:


 Feed analysis to minimize concurrence of two dominant fouling mechanisms
 Blending light and denser crude oils together while avoiding precipitation
 Further study of surface characteristics so as to fundamentally understand fouling
 Use of intermittent pulsed flow
 Feed at varying temperatures and pH values

These methods have shown promise in reducing fouling and had also resulted in
significantly improved HTCs that can allow small heat exchangers to be used instead.
Also, maintenance costs would be mitigated with these implementations.

Production of Hydrogen via Syngas Route 7-36


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.7 HEAT EXCHANGER SPECIFICATION SHEET


Heat Exchanger data sheet Equipment number (Tag) A-123
Description/Function Hydrogen Plant
Type/Class AES / R No. of units 1
Shells per unit 1 Connected in (parallel or series) 1 1
Surface per unit (m2) 351 Surface per shell (m2) 351
Performance of one unit
SHELL SIDE TUBE SIDE
Fluid circulating SMR Feed SMR Outlet
Total fluid entering (kg/hr) 183500 183500
IN OUT IN OUT
Vapor flow rate (kg/hr) 183500 183500 183500 183500
Liquid flow rate (kg/hr) - - - -
Non-condensables flow rate (kg/hr) - - - -
Temperature (K) 526 813 1125 879
Density (kg/m3) 9.258 4.031
Molecular weight 17.63 12.67
Viscosity liquid (kg/m.s) 2.002e-5 2.797e-5
Latent heat (kJ/kg) - -
Specific heat (J/kg.K) 2483 2964
Thermal conductivity (W/m.K) 0.067 0.183
Operating pressure (kPa) 2700 2655
Velocity (m/s) 26.7 32.6
Number of passes 2 2
Fouling factor (m2.K /W) 0.000176 0.000352
Pressure drop (kPa) 150 19.2
Heat transferred (kJ/hr) 1.30e+8 MTD (corrected) (K) 293
Overall U (W/m2.K) 351
Construction of one Shell
Maximum operating pressure (kPa) 3000 3000
Maximum operating temperature (K) 813 1125
Type of unit Tube pitch 0.0635 m Joint Strength weld
Tube material Carbon steel O.D (m) 0.0508 I.D (m) 0.04659 Length (m) 4.88
Shell material Carbon steel Diameter (Approx.) (m) 1.53
Tube Sheet material Carbon steel Baffle material Carbon steel
Corrosion allowance (m) Tube side 0.00211 Shell side 0.00211
Baffle cross C.S. Type Segmental Spacing (m), % Cut 0.642, 45

Baffle arrangement Nozzle arrangement


Remarks: Flared nozzle to reduce high inlet gas velocities.

Production of Hydrogen via Syngas Route 7-37


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

7.8 INTEGRATED HEN WITH PFD OF PROPOSED HYDROGEN PLANT

Figure 14: Integrated heat exchanger network with PFD of proposed hydrogen plant.

Production of Hydrogen via Syngas Route 7-38


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

APPENDIX A – STREAM DATA


Inlet Temp Outlet Temp MCp Enthalpy HTC Flowrate Effective Cp
(°C) (°C) (MW/°C) (kW) (W/m2°C ) (kg/h) (kJ/kg-°C)
SMR Feed To Heated SMR Cold 218.0 539.4 0.1264 40621.1 479 183495 2.48
Feed
SMR Outlet To Cooled Hot 851.9 353.9 0.1470 73234.72 471 183497 2.88
HTS Feed
NG Feed To Heated NG Cold 25.0 250.0 0.0325 7307.54 764 42828 2.73

Flue Gas To Stack Gas Hot 565.6 150.0 0.1062 44118.78 42 312845 1.22

Combustible Air To Cold 25.0 150.0 0.0853 10667.62 102 299742 1.02
Preheated Air

HTS Outlet To Cooled LTS Hot 418.3 220.0 0.1539 30506.41 546 207402 2.67
Feed

LTS Outlet To Cooled PSA Hot 238.8 50.0 0.1774 33501.16 2074 207402 3.08
Feed

Cold T In Cold T Hot T In Hot T Out dT Min dT Min


Cold Stream Hot Stream Load (kW) Area (m2)
(°C) Out (°C) (°C) (°C) Hot (°C) Cold (°C)
SMR Feed To Heated SMR Outlet To Cooled HTS
253.3 539.4 851.9 606.0 36159 519 312.6 352.7
SMR Feed Feed
NG Feed To Heated
25.0 250.0 Flue Gas To Stack Gas 263.3 194.5 7308 3269 13.3 169.5
NG
HTS Outlet To Cooled LTS
HP Steam Generation 253.3 254.3 418.3 263.3 23844 844 164.0 10.0
Feed
HP Steam Generation 253.3 254.3 Flue Gas To Stack Gas 565.6 263.3 32091 8859 311.3 10.0
Combustible Air To
25.0 80.3 Flue Gas To Stack Gas 194.5 150.0 4721 1368 114.2 125.0
Preheated Air
SMR Feed To Heated HTS Outlet To Cooled LTS
218.0 253.3 263.3 234.3 4462 1554 10.0 16.3
SMR Feed Feed
Combustible Air To HTS Outlet To Cooled LTS
80.3 106.1 234.3 220.0 2200 192 128.2 139.7
Preheated Air Feed
LTS Outlet To Cooled PSA
Cooling Water 32.2 48.9 217.7 50.0 29754 335 168.8 17.8
Feed
SMR Outlet To Cooled HTS
HP Steam Generation 253.3 254.3 606.0 353.9 37076 410 351.7 100.6
Feed
Combustible Air To LTS Outlet To Cooled PSA
106.1 150.0 238.8 217.7 3747 393 88.8 111.6
Preheated Air Feed

Production of Hydrogen via Syngas Route 7-39


CN 4120: Design II
Team 32: Sin Yew Leong (U046835M) HEN Unit Design Report

REFERENCE

1. Seider, W.D., Seader, J.D., Lewin, D.R. (2004). Product and Process Design Principles:
Synthesis, Analysis and Evaluation. 2nd Ed., John Wiley & Sons, Inc.
2. F.W. Dittus and L.M.K. Boelter, University of California, Publ. Eng., 2, 443 (1930
3. Bell, K.J., & Mueller, A.C. (2001). Wolverine Engineering Data Book II, Retrieved March
27, 2008, from Wolverine Tube Inc. Web site:
http://www.wlv.com/products/databook/databook.pdf
4. Hall, S.G., Ahmad, S., & Smith, R. (1990). Capital Cost Targets for Heat Exchanger
Networks Comprising Mixed Materials of Construction, Pressure Ratings and Exchanger
Types. Computers & Chemical Engineering, 14, 3, p. 319-335
5. Turton, R. et al (1998). Analysis, Synthesis and Design of Chemical Process. 2nd Ed.,
Upper Saddle River, NJ: Prentice Hall.
6. Economic Indicators. Chemical Engineering. Retrieved March 28, 2008 from Chemical
Engineering Web site:
http://www.che.com/business_and_economics/economic_indicators.html
7. Umeda, T., J. Itoh, J., & Shiroko, K. (1978). Heat Exchange System Synthesis. Chem. Eng.
Prog., 74, 70.
8. Shenoy, U.V. (1995). Heat Exchanger Network Synthesis : Process Optimization by
Energy and Resource Analysis. Houston: Gulf Pub
9. Linnhoff, B., & Hindmarsh E. (1983). The Pinch Design Method for Heat Exchanger
Networks. Chem. Eng. Sci., 38, 745
10. Chemical Engineering Design. 4th Ed., Oxford: Elsevier Butterworth-Heinemann
11. Branan, C. R. (2002). Rules of Thumb for Chemical Engineers : A Manual of Quick,
Accurate Solutions to Everyday Process Engineering Problems. 3rd Ed., Amsterdam; New
York: Gulf Professional Pub
12. Perry, R.H., & Green, D.W. (1997). Perry’s Chemical Engineers’ Handbook. 7th Ed.,
McGraw-Hill
13. Muller-Steinhagen, H. et al. (2007). Recent Advances in Heat Exchanger Fouling
Research, Mitigation, and Cleaning Techniques. Heat Transfer Engineering, 28, 3: pg. 173–
176

Production of Hydrogen via Syngas Route 7-40


CN 4120: Design II
Team 32 Economics & Profitability Report

Chapter 8 : COOLING TOWER

8.1 PROBLEM STATEMENT

The cooling tower in this hydrogen plant is designed to provide a continuous flow of cooling
water required for the condensation and elimination of water vapour in the outlet stream of
low temperature shift (LTS) reactor, before it is fed into the pressure swing adsorption (PSA)
column for purification of hydrogen and removal of carbon dioxide. The cooling duty of the
tower is found to be 2.975 ×104 KW . In order to meet this requirement, an induced draft
cooling tower with counter-flow pattern is designed.

The detailed design of this cooling tower would consist of the following sections:
• Physical dimensions of the cooling tower
• Cooling tower internals
• Material of construction
• Optimization and cost analysis

Production of Hydrogen via Syngas Route 8-1


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Team 32 Economics & Profitability Report

8.2 WORKING PRINCIPLES OF COOLING TOWER

Heat transfer in cooling towers occurs by two major mechanisms [1]: the transfer of sensible
heat from water to air by convection process and the transfer of latent heat by evaporation of
water.

Although sensible heat transfer due to temperature difference between the air and water
occurs, the extent of this heat transfer is much smaller as compared to the removal of heat
from water via latent heat of vaporization.(20% due to sensible heat:80% due to latent heat)

The governing equation for the heat transfer in cooling tower is the Merkel Equation [2],
defined to be

T1
KaV dT

=∫
L Cp h − ha
T2 sa

where Ka = volumetric air mass transfer coefficient ( lb air / hr ft 3fill )


_
V = specific fill volume ( ft 3fill / ft Base
2
Area )

_
2
L = loading factor ( lb H 2O / ft Base Area )

hsa = enthalpy of saturated air at water temperature (Btu/lb dry air)


ha = enthalpy of air stream (Btu/lb dry air)
T1 = inlet water temperature ( o F )
T2 = outlet water temperature ( o F )

The derivation of this equation ignores the mass transfer resistance from bulk water to the
interface, the effect of evaporation, and the temperature differential between the bulk water
and interface. It demonstrates that the driving force for the cooling process is the enthalpy
potential difference between the interfacial film and surrounding air.[3]

Production of Hydrogen via Syngas Route 8-2


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Team 32 Economics & Profitability Report

8.3 Preliminary Design

Before we can proceed with the actual design of the cooling tower, the different
configurations for cooling tower must be examined for its advantages and disadvantages in
order to make a choice the configuration that is going to be used in this design report.

8.3.1 Selection of cooling tower

Cooling towers can be classified according to the means by which air is supplied to the
towers, i.e., natural draft vs. induced or forced mechanical draft (fans) and according to
relative movement of air and water, that is, counter-flow or cross flow.

8.3.1.1 Justification to reject the use of natural draft tower

Natural draft or hyperbolic cooling tower depends on the natural draft created by the
difference in the density of the entering and leaving air for movement. Due to their large sizes,
they are often used for water flow-rates above 200,000gal/min.[3] Though it does not incur
any operating or maintenance cost for fans and experiences almost no recirculation of hot air
that could affect tower performance, it is not used in this design due to the following reasons:

1. The construction of hyperbolic cooling tower requires large plot space which results
in higher capital investment on land

2. Natural draft tower depends completely on atmospheric conditions. This implies


that water temperature is difficult to control and maintained, which might affect
downstream units that utilize the cooling water. In our case, the affected unit will be
the heat exchanger that makes use of cooling water to eliminate water vapout [4]

Production of Hydrogen via Syngas Route 8-3


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Team 32 Economics & Profitability Report

8.3.1.2 Justification to use induced draft tower

Mechanical draft towers can be either forced or induced draft, depending on the position of
the fans. Forced draft towers have the fans located at the base of the tower which push the air
through the fill while induced draft units have fans located on the top of the tower which pull
the air through the packing and discharge them vertically upward at high velocity.

Induced draft cooling tower is preferred over forced draft towers due to following factors:[5]

1. Unlike forced draft tower which is subjected to recirculation of hot humid


discharged air into the fan intake, the recirculation issue is completely avoided in
induced draft since the air is discharged upwards at high velocity.
2. The induced draft allows a more uniform distribution of air inside the tower.
3. The power requirement of the fan system in induced draft tower is about half that of
forced draft tower for the same capacity.
4. Compared to forced draft tower, induced draft tower require less initial cost to start
up, take up less space and have the capability to cool over wide range.

8.3.2 Comparison between counter-flow and cross-flow Pattern

For cooling towers, counter-flow pattern is preferred over cross-flow pattern mainly because:

1. For a tower of similar capacity, 20-50% less pumping head is required for counter-
flow cooling tower as compared to cross-flow tower. This implies that counter-flow
tower can operate at a lower cost. [6]
2. Unlike cross-flow tower, counter-flow tower does not experience recirculation,
which greatly reduces tower performance due to higher wet-bulb temperature. [6]
3. Under the same design condition, a counter-flow tower produces more cooling per
unit volume at a lower cost.[6]

Based on the above factors, counter-flow pattern is chosen for my design of cooling tower.

Production of Hydrogen via Syngas Route 8-4


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Team 32 Economics & Profitability Report

8.4 DETAILED DESIGN OF COOLING TOWER

(All calculations in this section is based on Reference 2)

8.4.1 Specification of cooling tower design parameters

8.4.1.1 Wet bulb temperature

Wet bulb temperature is the temperature of the air entering the cooling tower and is the
lowest temperature at which water can be cooled to theoretically. Since a counter-flow
induced draft tower is designed, it is valid to assume that there is no recirculation. Hence, the
wet bulb temperature is taken to be that at ambient condition.

Taking a conservative approach, the ambient wet bulb temperature is determined using the
maximum dry bulb temperature in Singapore

As of 2007,[7]
Average daily maximum dry bulb temperature = 31.1 oC
Mean relative humidity at 2 pm = 74%

From the psychrometric chart,


Ambient wet bulb temperature (t1) = 27.2 oC (81.0 o F )

8.4.1.2 Range

The range is defined to be the difference between the cooling tower water inlet (T1) and outlet
temperature (T2). Heuristic [8] assumes the maximum inlet temperature of cooling water to
be 120 o F (48.9 oC ) and cooling water exit temperature to be 90 o F (32.2 oC ) .

Hence,
Range = T1 – T2 = 120 – 90
= 30 o F = 16.7 oC

Production of Hydrogen via Syngas Route 8-5


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8.4.1.3 Cooling water requirement

From the Heat Exchanger Network Design, the cooling water duty is found from simulation
using HX-Net to be 2.975 ×104 KW . Hence, the amount of cooling water (L) required to
achieve this cooling load can be calculated by
Q
L=
C p (T1 − T2 )

T1 + T2
where Cp = Effective heat capacity of water at temperature .
2
2.975 ×104 × 3600
L= = 1.488 ×106 kg / hr
4.320(48.9 − 32.2)

8.4.1.4 Approach
Approach is defined to be the difference in temperature between the cooling water leaving the
tower and the ambient wet bulb temperature. As a general rule, the closer the approach to the
ambient wet bulb temperature, the more expensive the cooling tower due to increased size.
Approach = T2 – t1 = 90 – 81 = 9 o F = 5 oC

This approach is very close to the typical approach of 10 − 15 o F in most cooling towers.

8.4.2 Exit air temperature and water to air flow ratio (L/G)

8.4.2.1 Exit air temperature

For a given set of cooling tower design conditions, an optimum design of the outlet air wet-
bulb temperature exists. This is desired as it will result in minimum construction and
operating costs. A good correlation exists between the optimum exiting air temperature (t2)
and the inlet and outlet cooling water temperature. This correlation which is to be used as a
rule of thumb for design is as followed:
T1 + T2 120 + 90
t2 = = = 105 o F = 58.3 oC
2 2

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8.4.2.2 Water to air flow (L/G) ratio


L
The ratio of a cooling tower is the ratio between the cooling water and air mass flow rate.
G
Thermodynamically, the heat removed from the cooling water must be absorbed by the
L
surrounding air. Hence, the following energy balance can be used to evaluate the ratio:
G
LC p (T1 − T2 ) = G (h2 − h1 )

L (h2 − h1 )
=
G C p (T1 − T2 )

where h2 = Enthalpy of air-water mixture at the exit air temperature (kJ/kg dry air)
h1 = Enthalpy of air-water mixture at inlet air temperature (kJ/kg dry air)
Cp = Heat capacity of water at 25 oC
L (h2 − h1 ) (189.1 − 104.1)
= =
G C p (T1 − T2 ) 4.18(48.9 − 32.2)

= 1.219
Assumptions made: 1) Cooling water mass flow is relatively constant (little evaporation)
2) Sensible heat transfer from water to air is negligible

8.4.3 Cooling tower characteristic

Tower characteristic can be determined by the Chebyshev method [1], whereby


T −T  1 1 
T1
KaV dT 1 1

=∫ ≅ 1 2 + + + 
L Cp T2
hsa − ha 4  ∆h1 ∆h2 ∆h3 ∆h4 

where hsa = Enthalpy of air-water mixture at bulk water temperature (Btu/lb dry air)
ha = Enthalpy of air-water mixture at wet bulb temperature (Btu/lb dry air)
∆h1 = value of (hsa – ha) at T2 + 0.1(T1 – T2)
∆h2 = value of (hsa – ha) at T2 + 0.4(T1 – T2)
∆h3 = value of (hsa – ha) at T1 – 0.4(T1 – T2)
∆h4 = value of (hsa – ha) at T1 – 0.1(T1 – T2)

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1
T, o F hsa ( Btu / lb dry air ) ha ( Btu / lb dry air ) hsa − ha
∆h
90 55.93 44.80
93 60.28 48.46 ∆h1 = 11.82 0.0846
102 75.42 59.43 ∆h2 = 15.99 0.0625
108 87.76 66.74 ∆h1 = 21.02 0.0476
117 110.60 77.71 ∆h1 =32.89 0.0304
120 119.54 81.37

**Note that the enthalpy of air-water mixture increases 1 Btu multiplied by L ratio for every
o
1 F of cooling.
G

KaV 120 − 90

≅ ( 0.0846 + 0.0625 + 0.0476 + 0.0304 ) ≅ 1.688
L Cp 4

At this point, it should be noted that mechanical-draft cooling towers are usually designed for

KaV
L/G ratios ranging from 0.75 to 1.50 and the values of −
vary from 0.50 to 2.50
L Cp

consequently. Hence, the results obtained so far for the design of the cooling tower have been
satisfactory.

8.4.4 Loading factor

_
Loading factor ( L ), also known as specific water flow rate, is the recommended cooling
water flow rate per unit volume of tower cross-sectional area. A general rule for loading
factor is that for difficult cooling jobs (large cooling range and/or close approach), a lower
loading factor is used and vice versa. A graphical method is presented to determine the
loading factor.

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Method to obtain the loading factor from the sizing chart

1. A straight line is drawn first to connect the inlet and outlet water temperatures as
illustrated in the figure

2. Another line is drawn to intersect the first line at the wet-bulb temperature. This line.
would yield the water concentration or the loading factor L

** Note that the loading factor determined from this graph is lower than loading factor used with presently-used
fills. However, method for determining modern loading factor is proprietary information and is not available.

From the graph,


_
gal lbs
L = 2.35 2
= 1176 2
min . ft Base Area hr. ftbase area

kg
= 5746 2
hr.mbase area

Assumption made: Density of cooling water does not change with temperature (1000 kg/m3)

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8.4.5 Dimensions of Tower

8.4.5.1 Fill Height


_
The required fill or packing height Z is assumed to be equal to the specific fill volume V in
the Merkel equation. It can be calculated from the tower characteristic and loading factor.
The fill height (z) can be determined from the following equation:
− −
KaV L
z=( − )calc ×
L Cp Ka

Past literature studies show that Ka value varied from 49 to 152 with 100 ± 30 as the average
value. Since Ka is proprietary information, Ka is assumed to be 100 based on previously-
designed cooling tower.

Hence,
1.688 × 1176
z= = 19.85 ft = 6.05m
100

8.4.5.2 Base area

The required base area or cross-sectional area (B) can be determined from the below equation:
L 1.488 × 106
B= −
= = 260m2
L 5746

8.4.5.3 Fill volume

The fill volume (V) can be calculated by


V = B × z = 260 × 6.05 = 1570 m3

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8.4.6 Make-up Water Requirement

In the cooling tower system, water makeup is required to replace the cooling water which is
lost through evaporation, drift and blow-down.

8.4.6.1 Evaporation loss (E)

The evaporation rate is assumed to be 1.0% of the water flow rate for each 10 o F temperature
drop through the tower. Hence, evaporation loss is calculated as shown below:

 T −T 
E =  1 2  × 0.01× L( m3 / hr )
 10 

 120 − 90  1.488 × 106


=  × 0.01× ( 3
) = 44.64 m3 / hr
 10  10

8.4.6.2 Drift loss (D)

Drift is the entrained water in the tower discharge air. Drift loss is usually a function of the
drift eliminator design and typically varies from 0.1 to 0.2% of the water supplied to the
cooling water. Adopting a conservative approach, the drift loss is assumed to be 0.2% of the
circulating cooling water.
D = 0.002 × L(m3 / hr )

1.488 ×106
= 0.002 × ( ) = 2.98 m3 / hr
103

8.4.6.3 Blow-down (B)

Blow-down is the continuous or intermittent discharge of a small amount of the circulating


cooling water. Its purpose is to limit the increase in the solids concentration in the water due
to evaporation. Since chlorides remained soluble in the cooling water, the blow-down rate
can be determined from the cycles of concentration, which is the ratio of chloride content in
the circulating water to the chloride content in the makeup water as shown in the equation..
1
B = E( )− D
Cycle − 1

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Cycles of concentration in cooling tower operations typically range from 3 to 5 but for
conservative design, it is assumed to be 3.
Hence,
1
B = 44.64( ) − 2.98 = 19.34 m3 / hr
3 −1

8.4.6.4 Makeup water requirement (M)


The makeup water requirement is the summation of evaporation loss, drift loss and blow-
down.
M = E+D+B
= 66.96 m3 / hr

8.4.7 Power Requirement

Fans are essential for the function of induced-draft counter-flow cooling towers, so that air
can be forced to flow vertically upwards to be in contact and cool the process water. As this
circulating water is sprinkled down the tower by using nozzles, a pump is also required to
pump the water to the top of the tower for cooling. These two auxiliary units are the main
usage of energy for the operation of the cooling tower, and hence must be considered as a
factor in the design.

8.4.7.1 Pump power (Pp)

Pump power is determined from the following equation

L× Hp
Pp =
1.98 × 106 ×η
where L = Water flow rate (lbs H2O/hr
Hp = Pump head (ft)
η = Fan Efficiency (dimensionless, assumed to be 0.80)

H p = z + 10 = 19.85 + 10

= 29.85 ft = 9.10 m

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Hence,
1.488 ×106 × 2.20462262 × 29.86
Pp =
1.98 × 106 × 0.80
= 61.84 hp

8.4.7.2 Fan Power (PF)

An estimate of fan power requirement is obtained from the volume of moist air moved by the
fan. For induced draft towers, this estimate is based on the exit air temperature which is
58.3 oC (105 o F )

At the air exit temperature,


Saturated absolute humidity of the air-water mixture:
H2 = 0.0507 lbs H2O/lb dry air
Density of dry air:
42.6439 42.6439 3
ρ dry air = = = 0.0755 lbs / ft
t2 + 460 105 + 460
Density of water vapour:
26.6525 26.6525 3
ρ water = = = 0.9304 lbs / ft
( t2 + 460 ) × H 2 (105 + 460 ) × 0.0507
Density of air-water mixture:

(1 + H 2 ) ( ρdry air × ρ water ) (1 + 0.0507 )( 0.0755 × 0.9304 ) 3


ρ mixture = = = 0.0734 lbs / ft
( ρdry air + ρwater ) ( 0.0755 + 0.9304 )
Air flow rate:
L
G = L( ) −1 = 1.488 ×106 × 2.20462262 × (1.219)-1 = 2.69 × 106 lbs / hr
G
Air flow rate (actual cubic feet of air per minute)

F=
(1 + H 2 ) G = (1 + 0.0507 ) (2.69 ×106 ) = 6.418 ×105 acfm
60 ( ρ mixture ) 60 ( 0.0734 )

Assuming one hp is required for each 8000 actual cubic feet of air per minute moved by the
fan,
Fan power can be calculated by:
F 6.418 × 105
PF = = = 80hp
8000 8000

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8.5 COOLING TOWER INTERNALS

8.5.1 Liquid Distributor

The liquid distributor serves the purpose of ensuring good liquid distribution by maintaining
uniform flow of liquid through the column. The type of liquid distributor used is very much
dependent on the flow pattern of the cooling tower.

A pressure type system of closed pipe and spray nozzles, like the one seen in figure 1, is
usually necessary for the counter-flow configuration.

Counter-flow distribution system in operation

Pressure spray system is more susceptible to clogging and more difficult to clean, maintain or
replace. However, it contributes significantly to overall heat transfer and does not require
high pump head in larger tower.

As for cross-flow tower configuration, the gravity flow distribution system is more
commonly used whereby the supply water is elevated to the hot distribution basin above the
fill. From this basin, the water flow over the fill (gravity-induced) through metering orifices
located in the distribution basin floor. Although this type of distribution system can be easily
maintained, it does not contribute to overall mass transfer and tends to require a higher
pumping head. There is also a tendency for algae growth if the basin is not covered.

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8.5.2 Fill

The fill or packing is actually heat transfer surface that maximize water/air contact area and
increase the contact time between air and water for more effective heat transfer. Fill is
available in two types of design – the splash mode or the film mode.

Splash fill normally consists of horizontal slats in horizontal rows offset to one another to
cause the water to break up into droplets as it falls downward through the cooling tower. As
such, maximum exposure between the water surface and passing air is achieved. Splash fill is
characterized by reduced air pressure losses and is less conducive to clogging and can be
cleaned easily after a spill. However, it is very sensitive to inadequate support and must
remain horizontal and level. If sagging occurs, the water and air will channel through the fill
in separate flow paths, impairing the thermal efficiency greatly. [9]

On the other hand, film fill causes the water to flow in films over large vertical surface, thus
promoting maximum exposure to air. Film fill has the capability to provide more effective
cooling capacity within a given amount of space than splash fill. Film sheets are usually
spaced very close to each other. Due to the smaller passages, film fill is more sensitive to
plugging and makes the cleaning difficult if plugging do occurs. Hence in operations where
contamination by debris is possible, film fill should be avoided. [9]

8.5.3 Drift Eliminators

Drift Eliminators, as the name suggests, are used to remove entrained water droplets (also
known as drift) in the discharge air stream so as to prevent unnecessary water losses. The
separation is achieved by subjecting the discharge air to sudden change in flow direction.
Through the sudden directional change, a centrifugal force is created which cause the
entrained water droplet to deposit on the eliminator surface, from which it will flow back into
the tower.

Drift eliminator exists in many configurations but are usually classified according to the
number of directional changes or passes. More commonly found eliminators are the
“herringbone” type or the “honeycomb” type with labyrinth passage as shown in the figure
below.

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“Honeycomb” type drift eliminator

Tighter control for drift release is expected nowadays due to possible environmental impact
associated with it. Drift can cause Legionnaires disease when mist droplets containing the
bacteria are inhaled into the body.

8.5.4 Supports

Although framework of cooling tower is already supported by massive cross-section, it is not


unbendable. Operations of large fans at high horsepower can result in large torsional forces
which could affect the stability of the tower. Therefore, it is necessary to construct a support
to maintain the proper positioning of the mechanical equipment used. These supports can be
in the form of heavy wall torque tubes welded to the outskirts of steel framework.

8.5.5 Cooling tower basin

The primary function of the cooling tower basin is to collect the cooled water leaving the
tower and to provide a reservoir for the cooling water pumps. In addition, it also serves as the
primary foundation for the tower and is also the collecting point for foreign materials washed
out of the air by water. Hence it must provide easy access for cleaning, have adequate
drainage facilities and be equipped with screening to prevent entry of debris into the suction
side piping.

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To enhance the reliability of cooling tower, a minimum storage capacity should be provided
in the cooling tower basin to obtain the necessary time for corrective action during
emergency. Design practices worldwide recommend a minimum storage of 10 minutes.

8.6 MATERIAL OF CONSTRUCTION

A cooling tower must be able to withstand long duration dead loads imposed by the weight of
tower components, circulating water, snow and ice; as well as short term loads caused by
wind, maintenance and even seismic activities. Its design should be able to accommodate a
wide range of temperatures, a variety of external atmospheric conditions and internal pressure.
Corrosion caused by oxygenation and high humidity should also be taken into account.

Typical materials used are wood and steel. However, due to the above requirements of the
cooling tower, wood would not deem as a very suitable material. This is because although
wood is cheap and can last up to 30 years if it is well maintained, the drawback is that it is
susceptible to fungal and bacteria attack. Moreover, fungal and bacteria attack are more prone
to happen under the wet operating conditions of the cooling tower in a humid and wet tropical
country like Singapore. As a result of these factors, galvanized carbon steel was chosen as the
choice of material.

8.6.1 Liquid Distributor

Distribution systems are subjected to a combination of high temperature (hot water) and
oxygenation which are conditions favourable for corrosion. Hence, the material of
construction should be highly resistant to corrosion and erosion. Materials that are popularly
used include hot-dip galvanized steel, cast iron and redwood stave pipe. Because of the
relatively low pressure experienced by cooling tower piping, plastic can also be used for pipe
and nozzles construction. These plastic pipes are then reinforced with fibre for mechanical
strength.

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8.6.2 Fills
Treated wood lath (primarily Douglas Fir) is considered as material of choice for splash type
fill due to its strength, durability, availability and relatively low cost. However, plastic such
as PVC which naturally has low flame spread rate is fast gaining popularity and dominance
due to safety consideration (fire-resistance properties). This is especially the case in steel
framed cooling water where fire-proofing is compulsory

Splash Type Fill – Wood Splash Bar Splash Type Fill – Plastic Splash Bars

Film fill, on the other hand, can be made of any material that is capable of being fabricated or
molded into shaped sheets, with a surface suitable for channeling of air and water. Currently,
the most popular material is PVC because of its chemical inertness, good strength and light
weight properties, low flame spread rate and most importantly, it can be molded to different
shape easily.

8.6.3 Drift eliminator


Similar to the fill, the material used for eliminator should be corrosion-resistant. In the
industry, treated wood and various plastic (predominantly PVC) are material acceptable for
drift eliminator.

8.6.4 Mechanical support


Traditional material used for these supports include carbon steel, hot dip galvanized after
fabrication or stainless steel at a significant additional cost. It is important to note that
stainless steel is not necessary as the combination of heavy construction and galvanization is
enough to meet the requirement for support.

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8.7 COST ANALYSIS

8.7.1 Construction cost of for cooling tower

The number of tower units (TU) in a given cooling tower can be calculated by the following
equation:
TU = L( gpm) × Rating factor

The rating factor is a measure of cooling job difficulty and a linear correlation exists between
the rating factor and the tower characteristic:

KaV
Rating factor = 0.9964( −
)calc − 0.3843
L Cp

= 0.9964(1.688) − 0.3843 = 1.298


Hence,
1.488 × 106 × 4.40286754
TU = (1.298) = 8504
1000

Cost of each tower unit is assumed to be US$14.45 (in 1978 dollars)


Construction Cost (US $1978 ) = 14.45 × 8504
= US $122,879.97

To correct 1978 dollars to 2007 dollars, we need to know the CECPI value for 1978 and 2007
CECPI (2007) = 528.2
CECPI (1978) = 218.8
CECPI (2007)
Construction Cost (US $2007 ) = US $1978 ×
CECPI (1978)
528.2
= US $122,879.97 × = US $296, 641.68
218.8

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8.7.2 Operating Cost

The operating cost in the plant consists of two main components: the cost of makeup water
and the utility cost (electricity) that arises due to fans and pump operation.

8.7.2.1 Cost of makeup water

The cost of process water is assumed to be US$0.067 / m3

Plant operation time is taken to be 8000hours/year

Hence,
Cost of makeup water = 0.067 × 66.96 × 8000 = US $35,890.56 / yr

8.7.2.2 Cost of Electricity

The total power requirement is the summation of pump power and fan power

PTotal = PF + Pp = 62 + 81 = 143hp

Since electricity is sold at MW-h, the horsepower must be converted to MW-h


1 hp = 746 W
Hence,
143 × 746 × 3600
143 hp = = 384MWh
106

Since electricity cost is at US$100/MW-h

Electricity Cost = US $38, 400

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8.7.2 Optimization between the operating and construction cost

Optimization of the cooling tower is performed to minimize the operating and construction
cost of the cooling tower. The variable that is changed is the exit air temperature. From the
calculations shown above, it is clear that when exit temperature air temperature differ, the

L KaV
ratio, the tower characteristic − , the tower dimensions and the power consumption by
G L Cp

fan and pump will vary. The parameter that will not change during varying exit air
temperature is the makeup water requirement. Hence, it is not used as a guideline for
optimization.

Steps to perform optimization


1. An excel file is set up that contains all the equation used in the design of cooling
tower.
2. The exit air temperature is changed, and the construction cost and the operating cost
which is also the cost of electricity is monitored.
3. Five data point was tested, including the optimum temperature used as the initial
guess and the results were plotted in a graph

60000
700000
50000 600000
C o n s tr u c ti o n C o s t

500000
Operating Cost (US$)

40000
400000
30000
300000
20000 200000
100000
10000
0
0 95 100 105 110 115
95 100 105 110 115
Exit Air Temp(o F)
Exit Air Temp (o F)

Chart of Operating Cost (US$) vs. Chart of Construction Cost (US$) vs.
Exit Air Temperature Exit Air Temperature

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From these two plots, two observations can be made:

1. The operating cost, which is also the cost of electricity, decreases with increasing exit
temperature until around 43.3 oC (110oF) where it increases with increasing exit
temperature
2. The construction cost increases exponentially with increasing exit air temperature.

At the current moment, it is very difficult to consider whether 43.3 oC is the optimum
operating temperature because a lot of cost has not been factored into this optimization
investigation. These costs include the cost of auxiliary units such as fans and pumps which is
not included in the construction cost of the cooling tower, the cost for water treatment in term
of buying the additives.

With all these information, only then can we calculate the payback period to determine
whether it is worthwhile to switch to 43.3 oC. Hence, I shall adhere to the calculations in the
previous section.

8.8 ADDITIONAL CONSIDERATIONS TO COOLING TOWER DESIGN

8.8.1 Water Treatment

Cooling tower water treatment is necessary to minimize or eliminate: corrosion, scale and
biological fouling of heat transfer surface (in heat exchanger) which is caused by impurities
and minerals in the water. The difficulties caused by these impurities and minerals are
summarized in the table found in Appendix A [4].

8.8.1.1 Corrosion control

Corrosion is an electrochemical process that deteriorates metals exposed to water in the


presence of corrosive agents such as acids, oxygen, or bacteria. A common form of corrosion
is pitting.

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Some of the possible causes of corrosion include:


1. Process leaks into the cooling water
2. water flow velocity that is too low (causes deposits and fouling lending to corrosion)
or too high (causes erosion and corrosion)
3. low pH and high temperature

To reduce corrosion to an acceptable level, chemical corrosion inhibitors which form


protective films on heat transfer surface are most effective. Examples of corrosion inhibitor
include phosphates, organics, zinc, nitrites, and molybdate salts. Unfortunately, the use of
chromate, which is a reliable corrosion inhibitor, is prohibited due to environmental
constraints.[4]

8.8.1.2 Scale control

Scaling is characterized by the formation of hard, dense deposits on material surfaces. These
deposits impact heat transfer. Calcium carbonate, which is formed from the reaction between
calcium ions and bicarbonate, is the main scaling constituent.

The key to prevention of scale formation in a cooling system is to maintain a reasonable


water velocity and to use chemical additives (dispersants) in combination with blow-down to
keep impurities concentration below the level which causes deposits. Equipment such as sand
pressure filter which requires minimal operating and maintenance cost can also be used.

8.8.1.3 Biological control

Operating conditions in cooling tower are ideal for growth of biological matters. These
conditions that encourage microbiological growth include favourable water temperature (20
to 50°C) and pH, continuous supply of nutrients and sunlight. If biological growth becomes
uncontrolled and form large sticky agglomerations, it may lead to operating problems as
listed below:
1. Fouling of heat transfer surfaces by bacterial slimes, resulting in flow restrictions
and high process temperatures.
2. Reduced cooling tower efficiency due to algae, fungi, and bacterial slime growth in
the water distribution basin and fill area of the cooling tower.

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3. Corrosion
4. Clogging of water distribution nozzles.

Oxidizing biocides such as chlorine or sodium hypochlorite chlorine can be used to control
biological activity to prevent these operating problems from happening.

8.8.2 Environmental Concerns

Some of the environmental concerns with regards to cooling tower include:


1. Cooling tower blow-down is normally bypassed around major wastewater treatment
and discharged with treated wastewater.
2. Noise emission from fans and from the flow of cooling water over the tower may
require suppression if located near a community.
3. Spills and overflow of toxic and hazardous chemicals used for treatment of cooling
water must be contained.

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8.9 CONCLUSION
In the sections above, the design of the cooling tower is carried out together with the cost
analysis and optimization. The specification obtained from the detailed calculations are
summarized in the table below
Cooling Tower Data Sheet
Tower Model Induced Draft

Flow Pattern Counter-Flow

Cooling Water Mass Flow Rate 1.488 x 106 kg/hr

Ambient Wet Bulb Temperature 27.2ºC

Exit Air Temperature 58.3ºC

On-Tower Cooling Water Temperature (Inlet) 48.9ºC (120 ºF)

Off-Tower Cooling Water Temperature (Outlet) 32.2ºC (90ºF)

Approach 5ºC

Range 16.7ºC

L
Ratio 1.219
G

KaV
Tower Characteristic − 1.688
L Cp

kg
Loading Factor 5746 2
hr.mbase area

Tower Dimension
Fill Height, z 6.05m

Base Area, B 260 m2

Fill Volume, V 1570 m3

Make-up Water Requirement


Evaporation (1% for every 10 ºF) 44.64 m3/hr

Drift Loss (0.02%) 2.98 m3/hr

Blow-down 19.34 m3/hr

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Power Requirement
Pump Head 9.10 m

Pump Power 61.84 hp

Fan Power 80 hp

Material of Construction
Cooling Tower Stainless Steel

Liquid Distributor Hot-Dip Galvanized Steel

Fill PVC

Drift Eliminator PVC

Mechanical Support Hot-Dip Galvanized Steel

Cooling Basin Concrete


Cooling Tower Data Sheet

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REFERENCES

1. Perry's Chemical Engineers' Handbook, Green, Don W. et al, McGraw-Hill, New York,
6th Edition, 1999, Chapter 12

2. Stephen A. Leeper, Wet Cooling Towers: ‘Rule-of-thumb’ Design and Simulation, U.S.
Department of Energy; Idaho National Engineering Laboratory, EGG-GTH-5775, July
1981.

3. Cooling Towers: Design and Operation Considerations, retrieved on 28 March 2008 from
Chemical Engineering Tools and Information website:
http://www.cheresources.com/ctowerszz.shtml

4. G.B. Hill, E.J. Pring, Peter D. Osborn, Cooling Towers : Principles and Practice, London;
Boston: Butterworth-Heinemann, 3rd edition, 1990

5. J. D. Palmer, P.E., C.E.M. Evaporative Cooling Design Guidelines Manual. 2002 [cited
2008 March 10]; Available from:
http://www.emnrd.state.nm.us/ECMD/Multimedia/documents/EvapCoolingDesignManua
l.pdf.

6. Donald R. Baker, Howard A. Shryock, A Comprehensive Approach to the Analysis of


Cooling Tower Performance, Technical Bulletin R-61 P-13, reprinted from the Journal of
Heat Transfer, August 1961.

7. Climate and Air Quality, in Yearbook of Statistics Singapore, National Environment


Agency. p. 4

8. Seider W.D., Seader J.D., Lewin D.R. Product & Process Design Principles. Edition 2

9. John C. Hensley, Cooling Tower Fundamentals, SPX Cooling Technologies, Inc.,


Overland Park, Kansas USA, 2nd edition, 2006, retrieved on 1 April 2008 from SPX
Cooling Technologies website:
http://spxcooling.com/en/library/detail/cooling-tower-fundamentals/

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APPENDIX A IMPURITIES FOUND IN COOLING WATER

CHEMICAL
CONSTITUENT DIFFICULTIES CAUSED
COMPOSITION
Ca 2+ and Mg 2+ salts
Hardness Form scale deposit on heat transfer surface
expressed as CaCO3
Bicarbonate salts Form calcium carbonate scales; attack
Alkalinity
expressed as CaCO3 materials made of wood
React with calcium in the water, forming
Sulphate Sulphate ions SO4− calcium sulphate deposits on condensers and
coolers
Add to dissolved solids content and increase
Chlorides Chloride ions Cl −
corrosion potential of cooling water
React with calcium, magnesium and iron that
Silica Reactive Silica SiO2
is in water to form silicate deposits
Corrosion of copper and zinc alloys; Form
complex ions with zinc component in
Ammonia Ammonium ion NH 4+
corrosion inhibitors, rendering them
ineffective;
High concentration of dissolved solids causes
corrosion and increases precipitation of salts
Dissolved solids ---
which form scale deposits on heat transfer
surface
Suspended solids Settling occurs when velocity decreases;
(undissolved --- causes plugging, deposition in heat
matter) exchangers and enhance biological growth
Oxygen and carbon General corrosion and local pitting of all
O2, CO2
dioxide metal surfaces
Algae, bacteria,
--- Organic growth and slime deposits
fungi etc

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Chapter 9 : ECONOMICS & PROFITABILITY

9.1 INTRODUCTION

It is important to carry out a cost analysis on the design and selection of


equipment present in the chemical plant. Estimation of the initial cost of setting up the
plant is done following the development of the process using simulation software such as
HYSYS and MATLAB. Based on correlations and heuristics, we are then able to
determine dimensions of our equipment and consequently an estimated cost. In addition
to the cost of equipment, utilities cost can be obtained from HYSYS. A preliminary
gauge of the plant start-up cost can then be obtained. Following the finalization of the
plant design, we are able to approach a more realistic figure for the total cost, given the
availability of price information regarding the major units and auxiliary equipment from
the vendors.

An economic analysis follows next. Such an analysis is crucial because it enables


the management as well as the investors to assess the feasibility and profitability of the
plan before deciding whether or not construction of the plant should take place. Potential
returns of the plant are weighed against the risks that are involved.

For this part of the design project, total capital investments and total operating
cost are determined based on the correlation given by Turton [R1]. Revenues derived from
the sales of hydrogen are computed.

9.2 ASSUMPTIONS

1. The plant is to be located on Jurong Island, Singapore


2. The plant land is rented instead of being purchased. Rent rate (based on per
annum) is obtained from Jurong Town Council(JTC).
3. Operation time of the plant is 8,000 hours/year
4. Lifetime of the plant is 15 years, including construction time of 2 years.

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CN 4120: Design II
Team 32 Economics & Profitability Report

5. Growth is at the same rate as the total cost of production


6. Salvage value for the plant is 10% of FCI.
7. All products of the steam methane reforming process are sold in the market.
8. The company is using its own profits to fund the investment cost of this project
and no bank loan is taken. It is assumed that the company has sufficient cash flow
to bear the investment cost and no interest would be paid to the bank. Hence
hydrogen that is produced can be sold at a more competitive price in the market.
In the event that the company wants to free up cash flow to sustain operations or
make other investments, a bank loan can be considered.
9. Corporate tax in Singapore is given as 18%.

9.3 CAPITAL COSTS

The total capital investment in the chemical process plant is made up of two main
components: the fixed capital and working capital [R1], i.e.

Total Capital Investment = Fixed Capital + Working Capital

The fixed capital represents all costs associated with the construction of the plant.
All fixed capital components are depreciable (except for land). The working capital
represents initial investment required to finance the initial phase of the operation before
revenues from the project starts. The working capital is usually used to pay wages, raw
materials and contingencies. As the working capital must be recovered at the end of the
project, it is a non-depreciable item on the
cash flow statement.

9.3.1 Computations for Fixed Capital

A list of the fixed capital costs is shown in Table 9-1. The fixed capital
investments include direct and indirect costs, costs for contingency and fee, as well as
auxiliary facilities costs.

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CN 4120: Design II
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Fixed Capital costs


Direct expenses
• Equipment purchase cost
• Materials used for installation cost
• Labour cost resulting from equipment installation
Indirect expenses
• Transportation, Insurance and taxes expenses
• Construction Overhead
• Contractor engineering expenses
Contingency and fee
• Contingency – for use in unpredictable circumstances
• Contractor fee
Auxiliary facilities
• Land Purchase
• Yard improvement
• Auxiliary development
• Offsite facilities and Utilities
Table 9-1: Items under Fixed Capital Costs

The direct and indirect expenses can be expressed in terms of the Bare Module
Cost (CBM). The CBM is the sum of all direct and indirect expenses incurred. To compute
CBM, the following equation is used.

CBM = C po FBM (9-1)

where FBM is the Bare Module Cost Factor which accounts for the operating condition
and the material of construction. Cop is the purchased cost for base conditions (equipment
made of carbon steel and at atmospheric pressure)

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CN 4120: Design II
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Cop is given by Equation 9-2.


log10 C op = K1 + K 2 log10 A + K 3 (log10 A) 2 (9-2)

where A is the capacity parameter of the equipment.

When the capacity of the equipment lies outside the effective range of correlation,
the smallest possible capacity is used for cost calculations. For towers that have larger
volume than allowed, the costs are modeled as multiple columns in sequence.

To account for inflation, the fixed capital costs are inflated using the following
formula:

C I
= (9-3)
Cb I b

where Cb is the known cost in the base year when the index was (=397 in 2001)
I (= 595.1 in December 2007) is taken to be the cost index in the year where the cost is C

To calculate the fixed capital costs, CAPCOST is employed. The costs for each
equipment is present in Table 9.2

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Table 9.2 Equipment Schedule

Tag
Equipment Cost, CBM
Section No. in Function Quantity Dimensions required for costing
Name (USD)
PFD
Materials of construction Low-Alloy Steel A387
To further convert carbon
Pressure 25bar
monoxide and steam into o
R-103 LTS vessel 1 Temperature 220 C 1,370,000
hydrogen and carbon
Diameter 3.31m
dioxide
Height 5.07m
LTS
To remove condensate
LTS knock-out so as to prevent
D-101 1 Materials of construction Low-Alloy Steel A387 542,000
drum contamination of
downstream catalyst
Subtotal for LTS section 1,912,000
Materials of construction SS Clad
Pressure 1bar-25bar
o
V-101 PSA columns To purify hydrogen gas 8 Temperature 50 C 25,676,516
PSA
Diameter 3.00m
Height 8.5m
Subtotal for PSA section 25,676,516
Materials of construction Carbon steel
To provide cooling water Pressure 1bar
Cooling V-102 Cooling tower 1 940,844
as a source of cold utility
tower Effective mass transfer 2
area 733m
Subtotal for HTS section 940,844

Heat exchangers 4,895,966


Auxiliary
units* Expanders 4,476,000

Subtotal for Auxiliary units 9,371,966

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*Auxiliary units details are on following page:


Heat exchangers
2
Tag No. to PFD Cold streams Tube/shell Hot streams Tube/shell Area (m ) Cost, CBM (USD)
designation designation
Expanded SMR
Cooled LTS Feed 1 To
HX-101 Feed To Heated Shell Tube 1553.7 1,629,379
Cooled LTS Feed 2
SMR Feed 1
Heated SMR Feed
SMR Outlet To Cooled
HX-102 1 To Heated SMR Shell Tube 519.2 526,634
HTS Feed 1
Feed 2
HP Steam 1 Cooled HTS Feed 1 to
HX-103 Tube Shell 409.7 581,212
Generation Cooled HTS Feed 2
HP Steam 2 HTS Outlet To Cooled
HX-104 Tube Shell 843.5 1,124,770
Generation LTS Feed 1
Preheated Air 1 To Cooled LTS Feed 2 to
HX-105 Shell Tube 191.9 251,244
Preheated Air 2 Cooled LTS Feed 3
Preheated Air 2 To LTS Outlet To Cooled
HX-106 Shell Tube 392.5 415,586
Preheated Air 3 Knockout Drum Feed 1
Cooled Knockout Drum
HX-107 Cooling Water Shell Feed 1 to Cooled Tube 335 367,140
Knockout Drum Feed 2
Subtotal 4,895,966

Expanders
Item Item Quantity Material of construction Cost, CBM (USD)
SMR Feed 1 SS 3,300,000
E-101
Expander
Steam 1 SS 360,000
E-101
Expander
H2 1 SS 816,000
E-105
Expander
Sub Total 4,476,000

Total Bare Module Cost = USD 78,680,946

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9.3.2 Computations for Total Module Costs

Besides accounting for the total bare module costs, it is also necessary to compute the
contingency and fee costs so as to account for the total module costs. The contingency and
contractor fee costs are assumed to be 15% and 3% of the bare module cost respectively. Adding
these two costs to the total bare module cost will give the total module cost. Alternatively, the
total module cost can be calculated from [R1]:
n
CTM = 1.18∑ CBm , i (9-4)
i =1

The contingency and fee costs are tabulated in the following table.
Cost Item Cost(USD)
Contingency 11,893,090
Contractor Fee 2,378,618
Total Bare Module Cost 93,558,977
Total Module Cost 107,830,685
Table 9-10: Table for contingency and fee costs

9.3.3 Computations for Grassroots Costs (FCI)

The grassroots cost of the plant is calculated by adding the auxiliary facilities costs to the
previously calculated total module cost. The various auxiliary facilities costs is shown in Table
9-1. Since the plant designed is a new start-up, the grassroots cost is also equal to the fixed
capital investment (FCI).
As information on the various cost items is limited,grassroots cost is evaluated from [R1]:
n
CGR = CTM + 0.50∑ C oBM ,i (9-5)
i =1

= US$107,830,685 + 0.50 (79,287,268)


= US$147,474,319

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CN 4120: Design II
Team 32 Economic & Profitability

9.3.4 Computations for Working Capital

The typical amount spent on working capital ranges between 15% and 20% of the fixed
capital investments, FCI. For conservative estimate, a value of 20% of fixed capital investment is
assumed for the working capital. Therefore

Working Capital = US$147,474,319 x 20%


= US$29,494,864

9.4 MANUFACTURING COSTS

To estimate the manufacturing costs involved in this chemical plant, there are 3
categories of costs that are included. They are as follows:

1. Direct manufacturing costs: These costs represent operating expenses that vary with
production rate. When product demand decreases, production rate is also dropped below
the design capacity and there would be a decrease in the factors making up the direct
manufacturing costs.

2. Fixed manufacturing costs: These costs are independent of changes in production rate.
They include property taxes, insurance and depreciation. These costs are charged at
constant rates even when the plant is not in operation.

3. General expenses: These costs represent an overhead burden that is necessary to carry
out business functions. These include management, sales, financing and research
functions.

4. Land lease cost: Since the land is rented, it will not be included in the fixed capital
investment, but in the operating cost of the plant.

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CN 4120: Design II
Team 32 Economic & Profitability

Cost item Value


1. Direct manufacturing costs, DMC
Raw materials CRM
Waste treatment CWT
Utilities CUT
Operating labor COL
Direct supervisory and clerical labour 0.18COL
Maintenance and repairs 0.06FCI
Operating supplies 0.009FCI
Laboratory charges 0.15COL
Patents and royalties 0.03COM
Total DMC = CRM + CWT + CUT + 1.33COL + 0.03COM + 0.069FCI
2.Fixed Manufacturing Costs, FMC
Depreciation 0.1FCI
Local Taxes and Insurance 0.032FCI
Plant Overhead Costs 0.708COL + 0.036FCI
Total FMC = 0.708COL + 0.068FCI + Depreciation
3.General Expenses, GE
Administration Costs 0.177COL + 0.009FCI
Distribution and Selling Costs 0.11COM
Research and Development 0.05COM
Total GE = 0.177COL + 0.009FCI + 0.16COM
4. Land lease, CL
Total Costs = CRM + CWT + CUT + 2.215COL + 0.190COM
+ 0.146FCI + CL + depreciation
Table 9-10: Components for Costs Of Manufacture

Production of Hydrogen via Syngas Route 9-9


CN 4120: Design II
Team 32 Economic & Profitability

9.4.1 Operating labour costs, COL

The number of operators per shift, NOL, is calculated using the following equation:
N OL = (6.29 + 31.7 P 2 + 0.23 N np )0.5 (9-6)

where P is the number of processing steps involving the handling of particulate solids and Nnp
is the number of non-particulate processing steps handing steps and includes compression,
heating and cooling, mixing, and reaction. In general Nnp is given by:

N np = ∑ Equipment (9-7)

where equipment comprises of compressors, towers, reactors, heaters and exchangers, and
excludes pumps and vessels.

No. of towers 9
No. of reactors 3
No. of heaters 1
No. of exchangers 10
Nnp 23
Table 9-11: Number of equipment

Since the plant does not handle particulate solids, P = 0.


Therefore, NOL= (6.29 + 31.7(0)2 + 0.23(23))0.5 = 3.40

The following assumptions are made when calculating COL.


• The plant is operating 8000hrs/yr = 47.6weeks/yr
• Each operator works 5 shifts per week, and each shift is 8 hours, thus an operator
works 47.6 × 5 = 238 shifts per year
• Assuming plant operates 24hrs/day, there are 3 shifts in a day. Total number of
shifts per year = 8000/8 = 1000 shifts/yr
• Number of operators needed to provide this number of shifts = 1000/238 = 4.2
operators

Production of Hydrogen via Syngas Route 9-10


CN 4120: Design II
Team 32 Economic & Profitability

Hence, operating labour needed = 4.2 × NOL = 14.3 ≈ 15

COL (2001) = 15 × US$50,000 = US$750,000 /yr


COL (2007) = US$1,004,691/yr

9.4.2 Utility costs, CUT

9.4.2.1 Electricity

Below is the calculation for the electricity cost for cooling tower.
Cooling tower Electricity (hp)
Pump power 173.95
Fan power 225.87
Power 399.82
Table 9-12: Total Power for Cooling Tower

Below is the calculation for the electricity cost for furnace.


Furnace Electricity (hp)
Induced draft fan 25
Forced draft fan 30
Power 55
Table 9-13: Total Power for Furnace

Total power (hp) Total power (MW) Cost of electricity Total annual cost
454.82 0.339 US$100/MWh US$ 271,200
Table 9-14: Total power for plant

Total electricity cost per annum (2007) = US$ 271,200

Production of Hydrogen via Syngas Route 9-11


CN 4120: Design II
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9.4.2.2 Cooling water cost

The cost for cooling water used in the cooling tower and the heat exchangers are
calculated as follows:
Water makeup Volume (m3/hr)
Evaporative Loss 124.99
Drift Loss 8.34
Blowdown 54.15
Total water makeup 187.49
Table 9-15: Process water used for cooling tower

Given cost of water is 0.067 US$/m3,


Cost of water used for cooling tower = $100,494

Total volume of water (m3/hr) Cost of water US$/m3 Total annual cost (US$/yr)
4280.71 0.067 2,258,570
Table 9-16: Process water used for heat exchangers

Volume of water used for heat exchangers = 4280.71m3/hr


Cost of cooling water used for heat exchanger (2007) = US$2,258,570
CUT = US$(271,200 + 2,258,570 + 100,500)
= US$2,630,270

9.4.2.3 Waste treatment costs, CWT

In this plant, the waste water coming out of the LTS knockout drum should be treated.
The volume of wastewater flowing out of this knockout drum is 92.23m3/hr. The cost of treating
this water is US$41/1000m3 of waste water [R1].

Cost of treating LTS knockout drum waste water (2001) = 92.23 × 8000 ÷ 1000 × 41
= US$30,250

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CWT = US$(30,250 × (595.1 ÷ 394.3))


= US$45,657

9.4.3 Raw materials costs, CRM

The raw materials used in this plant are natural gas and high pressure steam.

Section of Raw Consumption Cost Annual cost of


plant material material (2007)
Feed to plant Natural gas 2603 kmol/h US$7.59/kmol US$158,054,160
HTS reactor HP steam 23910 kg/h US$33/tonne US$6,312,240
To SMR HP steam 140700 kg/h US$33/tonne US$37,144,800
Table 9-17: Raw materials used for the plant

Unit Type of catalyst Cost of Lifespan of Annual cost of


catalyst catalyst catalysts (2007)
HTS reactor Cr iron oxide US$109414 3 years US$36470
catalyst
LTS reactor Cu Zn oxide US$226800 3 years US$75600
catalyst
PSA reactor Activated carbon US$372372 3 years US$124124
and zeolite 5A
catalyst
Table 9-18 Cost for catalysts

CRM = US$(158,054,160 + 6,312,240 + 37,144,800 + 36,470 + 75,600 + 124,124)


= US$ 203,751,994

9.4.4 Land lease, CL

The land area required per year = 29400m2


From Jurong Town Corporation, the price of land rental at Jurong Island is $11.87psm per year.
CL = $29400 ×11.87 ÷1.3577
= US$257,036

Production of Hydrogen via Syngas Route 9-13


CN 4120: Design II
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9.4.5 Computation of manufacturing costs

To calculate COM, cost of manufacture, the following equations were used:


DMC = CRM + CWT + CUT +1.33COL + 0.069FCI + 0.03COM
FMC = 0.708COL + 0.068FCI + depreciation
GE = 0.177COL + 0.009FCI + 0.16COM
Thus, adding all 4 components together, we can solve for COM:
COM = 0.180FCI + 2.73COL + 1.23(CUT + CWT + CRM) + CL + depreciation

Cost item Cost (US$)


1. Direct manufacturing costs, DMC
Raw materials 203,751,994
Waste treatment 45,657
Utilities 2,630,264
Operating labour 1,004,692
Direct supervisory and clerical labour 180,845
Maintenance and repairs 8,848,459
Operating supplies 1,327,269
Laboratory charges 150,704
Patents and royalties 8,938,259
Total DMC = US$226,559,293
2.Fixed Manufacturing Costs, FMC
Local Taxes and Insurance 4,719,178
Plant Overhead Costs 6,020,397
Total FMC = US$10,662,888
3.General Expenses, GE
Administration Costs 1,505,099
Distribution and Selling Costs 32,773,615
Research and Development 14,897,098
Total GE = US$49,071,189
4. Land lease, CL = US$257,036
Total Manufacturing Costs, COMd (without depreciation) = US$301,540,961
Table 9-19: Computed values for Costs Of Manufacture

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CN 4120: Design II
Team 32 Economic & Profitability

9.4.6 Salvage value

Salvage value, S, represents the fixed capital investment of the plant minus the cost of the
land, at the end of the plant life. Assuming the salvage value of the property at the end of service
life is 10% of FCI.
Salvage Value, S = 10% of FCI = US$14,747,432

9.4.7 Depreciation

Depreciation is the reduction in value of equipment due to physical deterioration. Depreciation is


calculated using the straight line depreciation method as follows:
Depreciation , dk = [FCI-S]/n
= (147,474,319 - 14,747,432)/15
= US$8,848,459/yr

9.4.8 Revenues

Steam revenue
Steam is generated from the heat exchangers in the plant.
Steam generation revenue (2007) = US$67,987,243/yr

Electricity revenue
Below is the table showing the electricity generated by the expanders in this plant.
Assuming turbine efficiency = 70%,
Component Duty (kW) Electricity generated (kW) Revenue (US$)/yr
SMR feed expander 1787 1251 1,000,800
Steam expander 41.28 28.90 23,120
H2 expander 287.2 201.04 160,832
Total Revenue 1,184,752
Table 9-20: Total Electricity Generated Revenue

Electricity generated revenue (2007) = US$1,184,752/yr

Production of Hydrogen via Syngas Route 9-15


CN 4120: Design II
Team 32 Economic & Profitability

Hydrogen revenue
Component Output (m3/yr) Output (kg/yr) Unit Price (US$/kg)
Hydrogen 1250,000,000 110,925,000 2.43
Total Revenue 270,024,351
Table 9-21: Total Hydrogen Generated Revenue

Total revenue from Hydrogen, Steam and Electricity


= US$ 67,987,243 + 1,184,752 + 270,024,351
= US$ 339,196,346

9.5 PROFITABILITY ANALYSIS

To find out the profitability and feasibility of a designed plant, an analysis of the cash
flow diagrams will be useful. Discrete and cumulative cash flow diagrams provide a clear insight
to the investments and profits which are made for every year of the plant project. The time value
of money is also important concept for assessing the profitability of a plant. The value of money
differs with time due to the earning capability of the money. The difference in the value of
money with time is not due to inflation and does not include the purchasing power of money.
This is an important concept as the designed plant is to operate over a span of several years and it
is hence more accurate for our profitability analysis if the time value of money is taken into
consideration.

In this section, the designed plant is considered to be built over 2 years and a plant life of
13 years follows, making up a total of 15 years for economic analysis. The cumulative cash flow
diagram for this project is studied. At the same time, the price at which the produced hydrogen is
to be sold so as to obtain a 10% return on the investment on the plant over a total payback period
of 15 years will be investigated.

Production of Hydrogen via Syngas Route 9-16


CN 4120: Design II
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9.5.1 Land Cost

The land cost is usually an investment that is made to the plant at the building stage of the
plant. The piece of land may be rented for the purpose of building and running the plant over its
construction + operation lifespan, which is taken to be 15 years for this project. In this case, the
land is being rented for the plant to be located in Jurong Island, Singapore. Jurong Town
Corporation, JTC has provided the rental cost which is US$8.74/m2 for each rental year.

Taking account of the dimensions of the various units as well as the amount of land
required for auxiliary facilities, the total required land area of 29400m2 for our plant will cost
US$257,036/yr. This amount of yearly rental is to paid from the construction of the plant till the
end of the plant operating life.

9.5.2 After Tax Cash Flow

The sales revenue made from the produced hydrogen, electricity and steam is not the
profit made to the plant due to expenses such as manufacturing costs and depreciation as well as
payable income tax. The net cash inflow to the plant or cash profit to the plant is thus after tax
cash flow here the cost of manufacture, cost of land rental, depreciation and income tax have
been taken into account.

The price of the hydrogen would be determined in the profitability analysis to assure a
rate of return of 10% to the plant. Since the plant is to be built and operated in Singapore, the
taxes payable would follow the corporate tax regulations on profits in Singapore by the Inland
Revenue Authority of Singapore, IRAS. The tax regulations state that corporate tax rate would
be at 18% from 2008 onwards and tax exemption is only valid for companies with income lesser
or equal to S$300,000 [2]. Since the positive income generated by the plant yearly is more than
S$300,000, a tax rate of 18% will be imposed on the designed plant.

t=18% (9-8)

Production of Hydrogen via Syngas Route 9-17


CN 4120: Design II
Team 32 Economic & Profitability

This tax scheme is used to calculate the amount of tax payable. As income refers to the
net income to the organization, the percentage tax should be multiplied to the net value of
revenue taking away expenses which are the cost of manufacture without depreciation.

Income tax = (R - COMd –d)t (9-9)

The after tax cash flow to a plant is therefore

After tax cash flow = (R - COMd –d) (1- t) +d (9-10)

9.5.2 Rate of Return on Investment (ROROI)

The rate of return on investment of a project can be determined from the ratio of the
average net profit to the fixed capital investment excluding land cost. The average net profit can
be obtained from averaging the cumulative cash flow at the end of the project (after 15 years).

As the ROROI refers to the rate of return on investment in a project, a positive ROROI is
expected for a feasible project, hence the ROROI should ideally be as high as possible. ROROI
has been set to be 10% for this project.

9.5.3 Net Present Value (NPV)

The net present value is the cumulative discounted cash flow at the end of the project. A
non-negative NPV is required for a feasible project and hence is assumed to be zero. A non-
negative NPV indicates that the plant would at least have a rate of return that is equal to the
discount rate used in the calculation. For this work, we employ a NPV of 0 to back-calculate the
price of hydrogen which we should be selling at in the market.

9.5.4 Discounted Cash Flows in Project

Keeping the above cash flows of the project in mind, a cash flow table of the project can
be determined once the selling price of the hydrogen is set. To ensure a 10% return on the

Production of Hydrogen via Syngas Route 9-18


CN 4120: Design II
Team 32 Economic & Profitability

investment for the discounted cash flow for a payback period of 15 years, a price of the hydrogen
is set such that the return on investment for the discounted cash flow is 10% and taking the
cumulative discounted cash flow at the end of the whole project to be zero. The ‘Goal-Seek’
function under Microsoft Excel is employed for this purpose. Table 9-22 shows the cumulative
discounted cash flows for our designed plant.

Cumulative
End of Gross After tax cash Discounted
Investment Depreciation Discounted Cash
year, k Profit cash flow Cash Flow
Flow
0 -260599 - 0 -260599 -260599 -260599
1 -88484591 - 0 -88484591 -80440538 -80701137
2 -88484591 - 0 -88484591 -73127761 -153828898
3 0 8848459 28209037 24724133 18575607 -135253291
4 0 8848459 28209037 24724133 16886916 -118366375
5 0 8848459 28209037 24724133 15351741 -103014634
6 0 8848459 28209037 24724133 13956129 -89058505
7 0 8848459 28209037 24724133 12687390 -76371116
8 0 8848459 28209037 24724133 11533991 -64837125
9 0 8848459 28209037 24724133 10485446 -54351679
10 0 8848459 28209037 24724133 9532224 -44819455
11 0 8848459 28209037 24724133 8665658 -36153797
12 0 8848459 28209037 24724133 7877871 -28275927
13 0 8848459 28209037 24724133 7161701 -21114226
14 0 8848459 28209037 24724133 6510637 -14603589
15 44242296 8848459 72451333 61002816 14603589 0
Table 9-22: Cummulative discounted cash flows

By fixing cumulative discounted cash flow to be 0 at the end of 15 years, a selling price
of US$2.43/kg is obtained via the ‘Goal-Seek’ function.

Production of Hydrogen via Syngas Route 9-19


CN 4120: Design II
Team 32 Economic & Profitability

Fig 9-1: Cumulative Discounted Cash Flow Plot

As we can see from the graph above, a selling price of $2.43/kg for the hydrogen product
will enable us to get a cumulative discounted cash flow of zero after 15 years (2 Construction
years + 13 Operation years).

We next study the price of hydrogen which we have to sell at, if we are concerned with a
shorter discounted payback period, as illustrated in Fig 9-2.

As we can see from figure 9.2, if we would like to recover our capital investment just
after 1 year of operation, we will need to sell hydrogen at US$4.19/kg. An important assumption
made here is that all hydrogen that is produced will be sold and there will be no leftovers. Given
more years for the returns, the price of hydrogen can be set at a lower rate. This is better overall
so that hydrogen can be priced more competitively, in view of numerous other hydrogen
providers in the market.

Production of Hydrogen via Syngas Route 9-20


CN 4120: Design II
Team 32 Economic & Profitability

Fig 9-2: Price of Hydrogen over the number of years of operation

9.6 FEASIBILITY OF STORAGE FACILITIES FOR NATURAL GAS FEED

This portion of the report addresses the feasibility of an installation of storage tanks for
the natural gas feed, as a recommendation for future consideration.

For our design at present, the natural gas feed has been assumed to be provided by
vendors via pipes and on top of this, there will be no interruption in the provision of natural gas
by the vendors. Product hydrogen is not stored and exported immediately once produced, since
we have earlier made the assumption that every unit quantity of hydrogen will be able to find its
customer in the market.

Production of Hydrogen via Syngas Route 9-21


CN 4120: Design II
Team 32 Economic & Profitability

Realistically speaking however, it is unlikely that there will be perfect provision of


natural gas without any failures everyday around the year. 2 possible scenarios of failures in the
provision of natural gas are identified:
1. Temporary complete-termination of natural gas provision due to errors at vendor’s end
2. Fluctuations (less/more than the contracted amount) in the natural gas provision

Both scenarios result in potential losses for the plant. Hence installation of storage tanks for
stand-by natural gas feed can be a solution around these problems.

In making a cost analysis of the proposed storage tanks, the following assumptions are
made:
1. Interruptions in natural gas provision do not last not more than 3 days, hence designs for
3 days’ worth of natural gas feed are made
2. Should there be any identified emergency in natural gas provisions, stand-by natural gas
from the storage tanks will be utilized with immediate effect and there is negligible delay
associated with the operation of control components
3. Heaters, coolers and piping constitute 20% of tank equipment cost
4. Tanks are of floating-roof type

Given that 2603 kgmole/h gaseous natural gas feed is provided by the vendor at 25oC &
40 bar, the following has to take place in order to store liquid natural gas in the storage tanks:

Fig 9-3: Storage process of natural gas feed

Production of Hydrogen via Syngas Route 9-22


CN 4120: Design II
Team 32 Economic & Profitability

1. Natural gas feed at 25oC will be cooled to -87oC to transform the gaseous feed into liquid
form to facilitate storage in the tank. Temperature at which the gaseous feed will
liquidize, i.e. -87oC has been verified with HYSYS.
2. In the event of an emergency such that the stand-by natural gas has to be employed, the
liquidized form of natural gas will be heated up slowly and gradually, to avoid the
potential hazard of rapid expansion due to vaporization, and rupturing of the pipes as a
result. Natural gas in gaseous form can then be fed into the furnace.

The following calculations are made:

Feed rate of Methane Feed(kg/h) 42830.00


Density of Liquid Methane (kg/m3) 422.62
Volume of Liquid Methane (m3/h) 101.34
Total volume stored (m3) 7296.77

Table 9-23: Calculations for storage volume

Total volume of liquid methane (natural gas) to be stored = 7296.77m3 (3 days’ worth)
20% volume allowance has been made for the vaporization of liquid methane within tanks, as
well as the innage/outage of the tanks.

Total volume needed = 7296.77 x 1.2


= 8756.12m3

Designing each tank to have a dimension of 55m (Diameter) by 35m (Height),


volume of each tank = 3022.25m3

Hence 3 tanks are necessary.

Production of Hydrogen via Syngas Route 9-23


CN 4120: Design II
Team 32 Economic & Profitability

A proposed plot plan of the storage tanks is as follows:

Fig 9-4: Plot plan of storage tanks for natural gas feed

9.6.1 Capital Costs

Initial capital cost will constitute the 3 tanks as well as piping, heater and cooler.
Based on CAPCOST,

Cost for 1 tank = US$431,000


Cost for 3 tanks = US$431,000 x 3
= US$1,293,000

Cost for piping, heater and cooler has been taken to be 20% of tank costs.
Hence their cost = US$1,293,000 x 20%
= US$258,600
Total capital cost = US$1,293,000 + 258,600
= US$1,551,600

Production of Hydrogen via Syngas Route 9-24


CN 4120: Design II
Team 32 Economic & Profitability

9.6.2. Operating Costs

Land Area needed (m3) Unit cost for land (US$/m3.yr) Land Cost (US$/yr)
21,025 8.84 185,829
Table 9-24: Operating Costs

Total duty (MWh) Unit cost for electricity (US$/MWh) Total Electricity cost (US$/yr)
885 100 88,520
Table 9-25: Electricity Costs

9.6.3 Overall Costs

Cost for the 1st year constitutes the initial capital cost in addition to land rental cost and
utility (electricity) cost. The remaining years in the course of plant operation will only involve
the operation costs, i.e. land rental costs and utility cost.

Assuming a storage facility is erected together with the construction of the plant, starting
from Year 0 that is, the cost breakdown is as follows:

Cost for 1st year 1,825,949 US$


Cost for 2nd year 274,349 US$
Cost for 3rd year 274,349 US$
Cost for 4th year 274,349 US$
Cost for 5th year 274,349 US$
Cost for 6th year 274,349 US$
Cost for 7th year 274,349 US$
Cost for 8th year 274,349 US$
Cost for 9th year 274,349 US$
Cost for 10th year 274,349 US$
Cost for 11th year 274,349 US$
Cost for 12th year 274,349 US$
Cost for 13th year 274,349 US$
Cost for 14th year 274,349 US$
Cost for 15th year 274,349 US$
Total Cost for all 15 years 5,666,836 US$
Table 9-26: Costs for storage facilities over 15 years

Production of Hydrogen via Syngas Route 9-25


CN 4120: Design II
Team 32 Economic & Profitability

Making a conservative allowance of 40% to take care of any unforeseen expenses,


total cost of such a storage facility = US$5,666,836 x 1.4
= US$7,933,570

From Section 9.3.3, our fixed capital investment(FCI) for the main plant has been
determined to be at US$147,474,319.
If we were to build a storage facility to last for 15 years, it will constitute only

(7,933, 570/147,474,319) x 100%


= 5.4% of FCI

From an economic point of view, 5.4% is a fairly small percentage. From this cost
analysis, it can be seen that erection of the storage facility can be done at a cost which is only
around 1/20 times of the capital investment made into the parent steam-methane reforming plant,
rendering the former feasible as a project. As mentioned, the presence of such a storage facility
for stand-by feed will to some extent, provide the much-desired security if the plant management
is concerned with a steady provision of natural gas.

Similar to the main plant, a SHE analysis on the installation of storage tanks will have to
be conducted. This is especially necessary as the tank contents involve methane which is a highly
flammable substance. In view of the potential hazards associated with the feed, it is
recommended that the storage facility be sited at a safe distance away from the main steam-
reforming plant.

9.6.4 Economic Compensation

Despite the attractiveness of a feed-storage, for our design we have assumed provision of
natural gas via piping with no failures on any day of the year.

Production of Hydrogen via Syngas Route 9-26


CN 4120: Design II
Team 32 Economic & Profitability

To back the decision of employing no storage tanks in our design, we have made the
following important assumption:

Should there be any failure in feed-delivery, compensations can be sought from the vendor

This is in view of the potential losses that can result from the inavailability of the natural
gas feed. Such compensations due to disruptions in service should have already been pre-agreed
upon as part of the terms of contracts between the plant management and their vendors.

However, the economic losses that arise from such a undesirable scenario can be difficult
to quantify sometimes. Plant management may consider employing the services of the financial
specialists to come up with a closer estimation to the actual damages suffered from a disruption
in feed supplies.

9.7 RECOMMENDATIONS

Based on the preliminary economic analysis, in order for the plant to break even, the
plant has to sell its hydrogen at US$2.43/kg. This analysis assumes a required rate of return of
10%, 18% corporate tax on income, 15 years discounted payback period and that all products of
this steam-reforming operation will be able to be sold in the market.

A more detailed analysis will encompass the inflation factor, as it is expected that the
company will have to increase the price of hydrogen over the years, following the expected
increase in operating costs, i.e. cost of utilities as a result of increases in crude oil prices,
increased rent cost etc. Pricing of the hydrogen heavily depends on the pricing strategies of other
competitors in the market, and in the event the minimum price which hydrogen should be priced
at (i.e. US$2.43/kg for our case) is significantly lower than the market average, say US$2.80/kg,
the company may want to sell its hydrogen at a higher price. Every cent increase in hydrogen
prices generates corresponding increase in profits as well as reduces the number of years which

Production of Hydrogen via Syngas Route 9-27


CN 4120: Design II
Team 32 Economic & Profitability

the company needs to break even with the initial capital cost. Taking for example, if the
company chooses to price its hydrogen at US$2.70/kg, the company may actually require only 7
years for cumulative discounted cash flow to reach zero, as opposed to the 15 years necessary if
hydrogen is priced at US$2.43/kg. Hence, we can see that pricing of hydrogen depends a great
deal on the strategy which the company would like to employ:

1. Does the company want to gain substantial market share in the market by selling at a
rate way below market average?
2. Does the company want to recover all its investments in a shorter period by selling
hydrogen at a higher price, while still maintaining below market price?

A way to reduce the cost of manufacture, so as to increase the profit margins, is to reduce
the utility costs. Cogeneration facilities can be implemented so as to be self sufficient in the
production of electricity. However, the feasibility of this recommendation has to be determined
through detailed calculations of the fixed capital investment costs of these facilities.
On computations of the equipment costs, different vendors may have different quotes for
the required equipments. Therefore, rather than relying on simplified correlations (such as using
CAPCOST) to find the costs, it may be better to refer to the available catalogue from the vendors
for more current and realistic cost estimations. This is made possible with the advanced
telecommunication and readily available information from vendors working with firm’s parent
company.

Assuming that the designed plant is already in operation, in the event that all the above
recommendations do not lead to an accurate economic analysis that result in a positive NPV, the
firm can consider forming strategic alliance with some other firms that have prior experiences in
building similar plants, to reap the internal and external economies of scales possible with such
an alliance. Alternatively, the company may consider approaching Chemical Engineering
Consultancies for suggested improvements on the plant designs and operation procedures.

Production of Hydrogen via Syngas Route 9-28


CN 4120: Design II
Team 32 Economic & Profitability

Financial or risk-management consultancies may be approached for a better estimation of present


and future financial status for the company. Should there be a definite forecast of unhealthy
financial status for the company in time to come, a re-assessment of the pricing strategies and
operation contingencies may be crucial.

9.8 CONCLUSION

Based on the assumptions made, the preliminary economic analysis shows that it is
possible to build a profitable steam-methane reforming plant. If we are concerned with a required
rate of return of 10% where payback period is 15 years, we can price our hydrogen at
US$2.43/kg, which is close to the suggested range ($1.90/kg to $2.30/kg) of hydrogen prices
provided by NETL (National Energy Technology Laboratory) [3]. Our price is obtained using
the Goal-seek function under Microsoft Excel by equating Cumulated Discounted Cash Flow in
the 15th year to zero. Any pricing of hydrogen above this rate increases our profit margins,
reducing the number the years which full returns can be realized. Again, here we are making the
assumption that any hydrogen produced will be able to find its customer in the market.
Competitiveness of the price, as mentioned, depends largely on the pricing strategies of other
hydrogen vendors in the market.

Factors that will make this economic analysis a more realistic study have been mentioned
under the recommendation section. As highlighted earlier, making an accurate assessment of
these factors in our work is beyond our expertise and hence employing finance specialists to
perform these complicated tasks will be the recommended option. In addition, chemical
engineering consultants can be approached for suggestions and further optimization on the
overall design and operations. In any event of a disruption in natural gas provision via piping,
compensations can be sought from the vendors, and availability of a legal support may reduce
the complications that arise from such a scenario.

Production of Hydrogen via Syngas Route 9-29


CN 4120: Design II
Team 32 Economic & Profitability

REFERENCES

[R1]: Turton R., Bailie R.C., Whiting W.B. and Shaeiwitz J.A., “Analysis, Synthesis, and Design
of Chemical Process”, Prentice Hall, 2003

[R2]: Inland Revenue Authority of Singapore, http://www.iras.gov.sg/, retrieved on 12 April


2008.

[R3]: National Energy Technology Laboratory ,


http://www.netl.doe.gov/technologies/hydrogen_clean_fuels/systems_studies.html, retrieved on
12 April 2008

[R4]: Guthrie, K. M., “Data and Techniques for Preliminary Capital Cost Estimating”, Chem.
Eng., 1969

[R5]: Perry, R.H., and Green, D.W., “Perry’s Chemical Engineers’ Handbook”, 7th Edition,
McGraw Hill, New York, 1997.

[R6]: Peters, M. S., Timmerhaus, K. D., “Plant Design and Economics for Chemical
Engineers” McGraw Hill, USA, 1968.

[R7]: J.R. Couper et al., “Chemical Process Equipment: Selection and Design”, Elsevier, 2005.

[R8]: R.K. Sinot, “Coulson and Richardson’s Chemical Engineering”, Vol. 6, 4th Edition,
Oxford 2005.

[R9]: Jurong Town Council. JTC's Land Rents and Prices, Retrieved on 2 April 2008 at
http://www.jtc.gov.sg/products/land/industrialland/pages/index.aspx

Production of Hydrogen via Syngas Route 9-30


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Chapter 10 : SAFETY, HEALTH & ENVIRONMENT (S.H.E.)

10.1 INTRODUCTION

Safety is of paramount importance in the operation of any chemical facility. Many


industrial accidents, such as the infamous Bhopal incident, serve as poignant reminders of the
significance of safety measures in preventing the escalation of minor accidents into major
catastrophes. A safe plant would make both economical sense, and uphold a positive image of
the company as a responsible corporate citizen in this global new economy.

To cover all safety aspects of plant operation, the following studies have been carried out:

1. Hazard and Operability review on the operations of the Furnace/SMR integrated system

2. Plant layout of the plant to ascertain preliminary site area and required safety clearances

3. Possible issues related to the occupational safety and health of plant personnel

Furthermore, the possible impact that the operation of a hydrogen plant has on the
environment would also be investigated in this report. It is essential that possible pollutants are
minimized and mitigation measures are duly mapped out in the preliminary design of a chemical
facility. This would be effected with the implementation of a risk assessment matrix.

A product life cycle assessment on hydrogen would also be used as a tool to further
illustrate the environmental impact of the manufacture of hydrogen through the steam methane
reforming route.

Production of Hydrogen via Syngas Route 10-1


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

10.2 HAZARDS AND OPERABILITY STUDIES (HAZOP) REVIEW

A HAZOP study is used to identify the potential hazards in a chemical facility and is
generally an effective method to determine operational hazards in any facility [R1]. In this
preliminary design of a hydrogen plant, it was identified that the safe and functional operation of
the furnace and the SMR unit were crucial to the smooth running of subsequent downstream
units.

A key issue that involves the integrated furnace/SMR system would be the possibility of
explosion. This could arise because the integrated furnace/SMR system operates at the highest
temperature and pressure in the plant. Furthermore, the presence of volatile fuel gas/air mixtures,
coupled with methane from the natural gas feed and hydrogen formed after reaction in the SMR
unit could also be possible explosive hazards.

Hence a HAZOP study was employed to further investigate and analyze any potential
impediments to their safe operation. This was done with reference to the P&ID diagram
presented in the Chapter 11 on Instrumentation and Control.

Production of Hydrogen via Syngas Route 10-2


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Project Name: Production of Hydrogen via Syngas Route


Process: Steam Methane Reforming
Section: Steam Methane Reformer
Reference Diagram: Furnace & SMR P&ID

Table 10-1: HAZOP study for SMR preheated reactor feed


Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters
Preheated Flow 1A No 1. Control valves, FCV- 1. No SMR reaction 1. Installation of low 1. Regular operators’
Reactor 101, FCV-102 fail 2. Shutdown of flow alarm training
Feed close downstream units 2. Installation of 2. Review of
2. Controllers, FC-101, 3. Increase in redundant expander operating
FC-102 fail and close temperature of flue E-102 procedures for
valves gas proper pipeline
3. Three-way valves 4. Disrupt preheating of isolation
fails close other process streams 3. Regular
4. Plugging of upstream in convection section inspections and
piping maintenance of
5. Plugging in expander expander E-101
E-101 and E-102 and E-102, heat
6. Complete plugging of exchangers HX-
heat exchangers HX- 101 and HX-102,
101 and HX-102 piping, valves and
7. Operators’ error in fittings
isolating pipes for
maintenance
1B High 1. Control valve, FCV- 1. Increase in reactor 1. Installation of safety 1. Review of
101, FCV-102 fail pressure valves PSV-001, operating
open 2. Rupture of SMR 002 and 005 procedures for
2. Controller, FC-101, tubes, leading to 2. Flow indicators FI- proper pipeline
FC-102 fail and open furnace explosion 203 for flow isolation
valves 3. Lower conversion due monitoring 2. Regular
3. Flow indicator fails, to lowered residence inspections and
indicating low time maintenance of
4. Error in flow control 4. Increased corrosion of pipings, valves
ratio inner SMR tube and fittings

Production of Hydrogen via Syngas Route 10-3


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

5. Operator error in surface due to 3. Regular operators’


valve control increased flow training
6. Faulty safety valve, velocity
fails to open
1C Low 1. Control valves FCV- 1. Higher conversion 1. Installation of low 1. See 1B
101, FCV-102 fail rate due to longer flow alarm FLA-
partially open residence time 203
2. Controllers FC-101, 2. Lower throughput
FC-102 fail and open 3. Possible
valve partially sedimentation of
3. Flow indicator FT- contaminants in
101 fails, indicating pipeline
high
4. Plugging of heat
exchangers HX-101
and 102
5. Operator error in
valve control
6. Safety valves PSV-
001,002 and 005 not
tightly close
1D Reverse 1. Pressure build-up in 1. Hydrogen 1. Installation of check 1. Decrease the
SMR embrittlement in feed valves furnace firing rate
pipeline not 2. Flow indicator FI-
designated to carry 203 for flow
hydrogen monitoring
2. Damage to expanders 3. Installation of safety
E-101 and 102 valve PSV-005 at
the entrance to SMR
Pressure 1E High 1. Coking of catalyst 1. Increase in reactor 1. Installation of safety 1. Regular
2. See 1B pressure valve inspections and
2. Rupture of SMR 2. Installation of PI- maintenance of
tubes, leading to 101 and PI-102 to valves, pipings,
furnace explosion check for catalyst fittings and
abnormalities catalyst
through higher than 2. Review of current
normal pressure operating

Production of Hydrogen via Syngas Route 10-4


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

drop procedures to
check for
contributory
factors to coking
3. Consider using
medium pressure
steam to decoke
catalyst for
maintenance
1F Low 1. See 1C 1. See 1C 1. See 1C 1. See 1B

Temperature 1G High 1. Control valve fails, 1. Higher rate of catalyst 1. Installation of 1. Regular
leading to increased coking temperature inspections and
flow in the heating 2. Shorter catalyst life, indicator TT-101 maintenance of
stream in HX-102 leading premature 2. Installation of flow valve and
2. Inefficient expander changeout control valve FCV- expander
E-101 and 102, 103 on the heating 2. Increase in
leading to under stream generation of HP
expansion steam, which
3. Increased preheating effectively
of natural gas feed reduces preheating
of natural gas feed

1H Low 1. Control valve FCV- 1. Lower conversion in 1. Installation of 1. Regular


103fails, leading to SMR tubes with the temperature inspections and
decreased flow in the maintenance of indicator TT-101 maintenance of
heating stream in HX- furnace duty 2. Installation of flow valve and heat
102 2. Higher furnace duty control valve FCV- exchangers, HX-
2. Poor piping insulation required, which 103 on the heating 102
3. Shell-side fouling of reduces the operating stream 2. Decrease in
heat exchanger lifespan of the furnace generation of HP
4. Inadequate preheating 3. Increase usage of fuel steam, which
of natural gas feed gas feed effectively
increases
preheating of
natural gas feed

Production of Hydrogen via Syngas Route 10-5


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Composition 1I High 1. Wrong setting of flow 1. Increase in catalyst 1. Installation of 1. Regular inspection
of natural control ratio due to coking due to reduced controllers FC-101, and maintenance
gas operators’ error steam FC-102 of valves and
2. Controllers, FC-101, 2. Installation of controllers
FC-102 fail control valves FCV- 2. Regular operators’
3. Control valves FCV- 101, FCV-102 training
101, FCV-102 fail

1J Low 1. See 1I 1. Higher cost due to 1. See 1I 1. See 1I


large amounts of
steam being injected

Production of Hydrogen via Syngas Route 10-6


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Table 10-2: HAZOP study for SMR reactor effluent


Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters
Reactor Flow 2A No 1. Plugging of reactor 1. Shutdown of 1. Installation of low 1. Regular operators’
Effluent outlet downstream units flow alarm FLA- training
2. See 1A 204 2. Regular
3. Plugging of catalyst inspections and
maintenance of
catalyst, pipings,
valves and fittings
2B Low 1. Partial plugging of 1. See 1C 1. Installation of low 1. Regular
reactor outlet flow alarm FLA- inspections and
2. See 1B 204 maintenance of
pipings, valves
and fittings

Pressure 2C Low 1. High pressure drop 1. See 1H 1. Installation of PI- 1. Review of current
along tubes 101 and PI-102 to operating
2. Coking of catalyst check for catalyst procedures to
abnormalities check for
through higher than contributory
normal pressure factors to coking
drop 2. Consider using
medium pressure
steam to decoke
catalyst for
maintenance
Temperature 2D High 1. Increased furnace 1. Coking of pipelines 1. Installation of 1. Reduce furnace
firing and downstream units temperature firing
2. Corrosion of pipes indicator, TI-106
due to high
temperature
2E Low 1. Decreased furnace 1. Low conversion of 1. See 2D 1. Increase furnace
firing natural gas to firing
hydrogen
Composition 2F High 1. Low reaction 1. Eventual product off 1. Installation of 1. Monitoring of

Production of Hydrogen via Syngas Route 10-7


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

of natural temperature specification methane analyzer temperature and


gas 2. High flow rate, A-004 adopting
leading to shorter 2. Installation of necessary
residence time temperature rectifications
3. Possible deactivation indicator TI-106 2. Consider using
of catalyst medium pressure
steam to decoke
catalyst as regular
maintenance
3. Catalyst
changeout to be
carried out if
necessary

Production of Hydrogen via Syngas Route 10-8


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Project Name: Production of Hydrogen via Syngas Route


Process: Combustion of Fuel Gas
Section: Furnace (Radiant Section)
Reference Diagram: Furnace & SMR P&ID

Table 10-3: HAZOP study for furnace (radiant section) fuel gas feed
Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters

Fuel Gas Flow 3A No 1. Control valve fails 1. Flame extinguished 1. Availability of 1. Regular
Feed close due to lack of fuel make-up fuel gas to inspections and
2. Controller fails and supply ensure continuous maintenance on
closes valve 2. Pressure build-up supply valves, pipings and
3. Complete plugging of upstream of blockage 2. Installation of low fittings
fuel gas feed line / closure flow alarm FLA- 2. Regular operator
4. Operators’ error in 3. Little or no 201 training
isolating pipe for conversion attained 3. Review standard
maintenance in SMR operating
5. Rupture of feed line 4. FCV-108 will close procedure for
6. Opened safety valve and lead to pressure pipeline isolation
PSV-012. All flow buildup on preheat air 4. Shut down of air
redirect to safety line blower B-101 in
valve the event of
pressure build-up
5. Adopt evacuation
procedures for fuel
gas release
3B High 1. Control valve (Main 1. Increase in 1. PSV-012 to relieve 1. Regular
Fuel gas line) fails temperature of flue any excess gas to inspections and
open gas flare maintenance of
2. Controller FIC-05 2. Thermal creeping of 2. Control valve valves, indicators,
fails and opens valve furnace tubes and pipings and
3. Error in flow meter walls fittings
FT-105 readings; 3. Unneeded usage of 2. Shutdown of fuel
indicating low additional fuel gas gas to prevent pipe
4. Control valve fails and air rupture

Production of Hydrogen via Syngas Route 10-9


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

(Make-up CH4) open 4. Rupture of pipeline 3. Adopt emergency


5. Faulty safety valve due to high pressure shutdown
PSV-012, fails to 5. Flame impingement procedures
open of tubes due to 4. Adopt evacuation
unstable flame procedures for fuel
gas release

3C Low 1. Control valve fails 1. Insufficient flame 1. Availability of 1. Regular


partially open / close height due to low fuel make-up fuel gas to inspections and
2. Controller FIC- 05 supply ensure continuous maintenance on
fails and opens / 2. Optimal SMR supply valves, pipings,
closes partially conversion not 2. Installation of low indicators and
3. Partial blockage / achieved flow alarm FLA- fittings
leakage of fuel gas 3. Pressure build-up 201 2. Adopt evacuation
feed line upstream of blockage procedures for fuel
4. Error in flow meter / closure gas release
FT-105 readings; 4. Sedimentation of
indicating high contaminants along
5. Safety valve PSV-012 the piping due to low
not tightly closed fuel gas flow
3D Reverse 1. Pressure build-up in 1. Occurrences of 1. Installation of check 1. Regular
furnace backfiring valve inspections and
2. Installation of flame maintenance of
arrestor check valve and
flame arrestor
Pressure 3E High 1. Control valve fails 1. Increase in 1. PSV-012 to relief 1. See 3B
open temperature of flue any excess gas to
2. Controller FIC-05 gas flare
fails and opens valve 2. Thermal creeping of
3. Pressure indicator furnace tubes and
fails, indicating low walls
4. Faulty safety valve 3. Unneeded usage of
PSV-012, fails to additional fuel gas
open and air
4. Rupture of feed line
due to overpressure
5. Excess flow to

Production of Hydrogen via Syngas Route 10-10


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

furnace resulting in
unstable flame and
flame impingement
3F Low 1. Control valve fails 1. See 3C 1. See 3C 1. See 3C
partially open / close 2. Occurrences of
2. Controller FIC-05 backfiring
fails and opens /
closes partially
3. Partial blockage /
leakage of fuel gas
feed line
4. Error in flow meter
FT-105 readings;
indicating high
5. Safety valve PSV-
012not tightly closed
Temperature 3G Low 1. PSA malfunction 1. Lower furnace 1. Install temperature
efficiency indicator
Composition 3H High 1. Deactivation of 1. Unstable flame 1. Installation of safety 1. Changeout of
of H2 catalyst in PSA leading to possible valve PSV-012 catalyst in PSA if
flame impingement necessary
3I Low 1. PSA purge too low 1. Insufficient flame 1. Introduction of
height due to low fuel makeup fuel gas
supply
2. Optimal SMR
conversion not
achieved

Production of Hydrogen via Syngas Route 10-11


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Table 10-4: HAZOP study for furnace (radiant section) preheated air feed
Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters

Preheate Flow 4A No 1. Control valves fails 1. Flame extinguished 1. FI-108 to indicate 1. Regular
d Air close due to lack of oxygen flow inspections and
Feed 2. Controller FIC-107 supply 2. FCV-108 to control maintenance of
fails and closes 2. Pressure build-up flow pipings, valves
valves upstream of blockage 3. Installation of low and fittings
3. Loss of air supply due / closure flow alarm FLA-202 2. Regular
to damaged air 3. Unneeded usage of inspections and
blowers, B-101, B- fuel gas maintenance of
102 4. Little or no SMR blower
4. Complete blockage of conversion attained 3. Regular operator
air feed line 5. Fuel gas released to training
5. Operators’ error in the environment due 4. Review of
isolating pipe for to incomplete operating
maintenance combustion procedures for
6. Rupture of air feed proper pipeline
line isolation

4B High 1. Control valve fails 1. Excessive flame 1. FI-108 to indicate 1. Regular


open height flow inspections and
2. Controller FIC-107 2. Pressure build-up in 2. FCV-108 to control maintenance of
fails and opens furnace flow pipings, valves
control valves and fittings
3. Error in flow control 2. Regular operator
ratio training
4. Operators’ error
5. Error in flow meter
FT-107 and 202
readings; indicating
low
4C Low 1. Partial plugging of 1. Fuel gas released to 1. FI-108 to indicate 1. Regular
control valves the environment due flow inspections and
2. Partial loss of air to incomplete 2. FCV-108 to control maintenance of

Production of Hydrogen via Syngas Route 10-12


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

supply due to combustion flow pipings, valves


damaged blower 2. Optimal SMR 3. Installation of low and fittings
3. Control valve FCV- conversion not flow alarm FLA-201 2. Regular operator
107 fails to respond achieved training
4. Controller FIC-107 3. Pressure build-up
fails to respond upstream of blockage
5. Piping or fitting / closure
leakage / partially
blocked
6. Error in flow control
ratio
7. Operators’ error
8. Error in flow meter
FT-107 and 202
readings; indicating
high
4D Reverse 1. Pressure build-up in 1. Occurrences of 1. Installation of check 1. Regular
furnace backfire valve inspections and
2. Installation of flame maintenance of
arrestor check valve and
flame arrestor

Pressure 4E High 1. CV fails open 1. Pressure buildup 1. Installation of relief 1. Regular


2. Controller FIC-107 within piping, leading valve inspections and
fails and opens to rupture 2. FI-108 to indicate maintenance of
control valves 2. Excess flow to flow valves, indicators,
3. Pressure indicator furnace leading to 3. FCV-108 to control and blower
fails unstable flame flow
4. Blower E-101 and
102 operating higher
than normal
4F Low 1. See 4C 1. Occurrences of 1. Install low flow 1. Regular
2. See 4E.2 backfire alarm FLA-202 inspections and
2. Insufficient flame 2. FI-108 to indicate maintenance of
height or flow pipings, valves
extinguished flame 3. FCV-108 to control and fittings
flow

Production of Hydrogen via Syngas Route 10-13


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Table 10-5: HAZOP study for furnace (radiant section) flue gas effluent
Study Process Item Deviations Possible Causes Possible Consequences Safeguard Actions Required
Node Parameters

Flue Gas Flow 5A No 1. Malfunction of all 1. Reduced steam 1. Installation of peek 1. Regular checks
Effluent burners generation holes via peek holes on
2. Complete blockages 2. Reduced preheating burning
of fuel gas and air of natural gas 2. Regular inspection
feeds 3. 3. Reduced and maintenance
preheating of air of piping for fuel
gas & air feeds
5B High 1. Higher than normal 1. Rupture of 1. Control valves that 2. Lower feed rates
fuel gas feed convection section control fuel gas and fuel gas and air
2. Higher than normal due to pressure build- air feeds
air feed up
2. Collapse of tubes in
convection section
5C Low 1. Malfunction of 1. Reduced steam 1. Installation of peek 1. Regular checks
burner(s) generation holes via peek holes on
2. Malfunction of 2. Reduced preheating burning
ignition source of natural gas 2. Regular inspection
3. 3. Reduced and maintenance
preheating of air of piping for fuel
gas and air feeds
Pressure 5D High 1. See 5B 1. See 5B 1. See 5B 1. See 5B
5E Low 1. See 5C 1. See 5C 1. See 5C 1. See 5C
Temperature 5F High 1. High air / fuel gas 1. Overheating and 1. Installation of 1. Lower feed rates
flow rates weakening of tubes in control valves that of fuel gas and air
2. Inefficient heat convection section control fuel gas and 2. Lower
transfer due to SMR 2. Cracking of furnace air feeds combustible air
tube degradation and walls temperature
fouling 3. Formation and
3. High temperature of emission of NOx due
combustible air feed to higher temperature
within furnace
4. Increased preheating

Production of Hydrogen via Syngas Route 10-14


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

of other process
streams in convection
section, leading to
process disturbances
in other units
5G Low 1. Low air / fuel gas 1. Less steam 1. Installation of 1. Regular checks
flow rate generation and control valves that via peek holes on
2. Inefficient furnace preheating of other control fuel gas and burning
burning process streams in air feeds 2. Regular inspection
3. Low temperature of convection section, and maintenance
combustible air leading to process of piping for fuel
disturbances in other gas and air feeds
units 3. Increase
temperature of
combustible air
Composition 5H High 1. Incomplete 1. Furnace flooding 1. Installation of CO 1. Lower fuel flow
of CO combustion of fuel leading to afterburn and O2 analyzer in rate.
gas in convection section the convection 2. Slowly increase
and possible section. combustible air
explosion. flow rate.
2. Emission of CO and
fuel gas to the
atmosphere

Production of Hydrogen via Syngas Route 10-15


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Project Name: Production of Hydrogen via Syngas Route


Process: Heat Exchange of Flue Gas
Section: Furnace (Convection Section)
Reference Diagram: Furnace and SMR P&ID

Table 10-6: HAZOP study for furnace (convection section) condensate


Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters

Condens Flow 6A No 1. Control valve FCV- 1. No steam generation 1. Installation of 1. Regular inspection
ate 104 fails close to buffer the flue gas bypass valve and maintenance
2. Controller FC-104 temperature 2. Installation of flow of valves,
fails fluctuations controller FC-104 controllers and
3. Bypass valve fails 2. Too much preheating and valve FCV-104 indicators
close of other process 2. Regular operator
4. Low temperature streams in convection training
reading on section, leading to 3. Review of current
temperature indicator disturbances in the operating
TE-104 other process units procedures
5. Operator error in 3. Possible creeping of
isolation of piping for steam generation tube
maintenance in convection section
4. Stack gas
temperature would be
elevated
6B High 1. Control valve FCV- 1. Rupture of steam 1. See 6A 1. See 6A
104 fails open generation tube in
2. Controller FC-104 convection section
fails 2. Too little preheating
3. Bypass valve fails of other process
open streams in convection
4. High temperature section, leading to
reading on disturbances in the
temperature indicator other process units
TE-104 3. Stack gas
temperature would be

Production of Hydrogen via Syngas Route 10-16


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

decreased, leading to
acid corrosion issue
in the stack
6C Low 1. Control valve FCV- 1. Little steam 1. See 6A 1. See 6A
104 fails partially generation to buffer
close the flue gas
2. Controller FC-104 temperature
fails fluctuations
3. Bypass valve fails 2. Too much preheating
partially close of other process
4. Low temperature streams in convection
reading on section, leading to
temperature indicator disturbances in the
TE-104 other process units
5. Operator error in 3. Possible creeping of
isolation of piping for steam generation tube
maintenance in convection section
4. Stack gas
temperature would be
elevated
Pressure 6E High 1. Control valve FCV- 1. Rupture of steam 1. See 6A 1. See 6A
104 fails open generation tube in
2. Controller FC-104 convection section
fails 2. Too little preheating
3. Bypass valve fails of other process
open streams in convection
4. High temperature section, leading to
reading on disturbances in the
temperature indicator other process units
TE-104 3. Stack gas
temperature would be
decreased, leading to
acid corrosion issue
in the stack
6F Low 1. Control valve FCV- 1. Little steam 1. See 6A 1. See 6A
104 fails partially generation to buffer
close the flue gas

Production of Hydrogen via Syngas Route 10-17


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

2. Controller FC-104 temperature


fails fluctuations
3. Bypass valve fails 2. Too much preheating
partially close of other process
4. Low temperature streams in convection
reading on section, leading to
temperature indicator disturbances in the
TE-104 other process units
5. Operator error in 3. Possible creeping of
isolation of piping for steam generation tube
maintenance in convection section
4. Stack gas
temperature would be
elevated

Production of Hydrogen via Syngas Route 10-18


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Table 10-7: HAZOP study for furnace (convection section) natural gas feed
Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters

Natural Flow 7A No 1. Disruption of supply 1. Discharge of natural 1. Ensure duplicity in 1. Regular inspection
Gas Feed 2. Pipeline rupture gas into environment supplies and maintenance
2. No reaction in SMR of supply
3. Higher preheating of pipelines
combustible air 2. Increase the
4. Elevation of stack amount of steam
gas temperature generation to
offset the increase
in preheating of
combustible air
and stack gas
temperature
7B High 1. Surges in supply 1. Rupture of natural 1. Installation of safety 1. Consider the
gas tubes in valve possible
convection section, installation of feed
leading to possible surge drum to
furnace explosion regulate the flow
2. Less preheating of of natural gas and
combustible air eliminate any
fluctuations

7C Low 1. Fluctuations in 1. See 7A.1 1. See 7A 1. See 7A


natural gas feed flow 2. Lower SMR
2. See 7A throughput
Pressure 7E High 1. See 7B 1. See 7B 1. See 7B 1. See 7B

7F Low 1. See 7C 1. See 7C 1. See 7C 1. See 7C

Production of Hydrogen via Syngas Route 10-19


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Table 10-8: HAZOP study for furnace (convection section) combustible air feed
Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters

Combust Flow 8A No 1. Loss of air supply 1. Elevation of stack gas 1. Availability of 1. Periodic cleaning
ible Air due to damaged air temperature redundant blower, or replacement of
blowers, B-101 2. Flame extinguished B-102 air filter
2. Complete blockage of due to lack of oxygen 2. Regular
air feed line supply inspections and
3. Complete plugging of 3. Little or no SMR maintenance of air
air filter conversion attained blowers

8B High 1. Accidental operation 1. Decrease in stack 1. Installation of 1. Regular operator


of two blowers B-101 temperature, leading safety valve training
and 102 to possible acid 2. Review of blower
2. Safety valve PSV- corrosion in the stack operating
010 fails to open 2. Rupture of air procedures
pipelines in the
convection section,
leading to possible
ignition of residual
fuel gas
8C Low 1. Damaged blower, B- 1. Optimal SMR 1. Availability of 1. See 8A
101 resulting in conversion not redundant blower,
reduced air flow achieved B-102
2. Partial blockage of air 2. Elevation of stack gas
filter temperature
3. Partial plugging of air
feed line
Pressure 8E High 1. See 8B 1. See 8B 1. See 8B 1. See 8B

8F Low 1. See 8C 1. See 8C 1. See 8C 1. See 8C

Production of Hydrogen via Syngas Route 10-20


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Table 10-9: HAZOP study for furnace (convection section) stack gas
Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters

Stack Temperature 1A Low 1. Too much heat 1. Condensation of acid 1. Installation of 1. Lower rate of
Gas transfer to process gases, leading to temperature steam generation
and utility streams in corrosion in stack indicator, TI-105 2. Increase flue gas
convection section temperature by
2. Low flue gas increasing rate of
temperature from burning
radiant section

Production of Hydrogen via Syngas Route 10-21


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Project Name: Production of Hydrogen via Syngas Route


Process: Heat Exchange of Flue Gas
Section: Furnace
Reference Diagram: Furnace & SMR P&ID

Table 10-10: HAZOP study for furnace


Study Process Item Deviations Possible Causes Possible Consequences Safeguards Actions Required
Node Parameters
Furnace Pressure 10A High 1. Faulty control system, 1. Rupture of SMR 1. Installation of flame 1. Regular
causing stack damper tubes, leading to arrestor inspections and
to remain closed furnace explosion 2. Installation of high maintenance of
2. Increase in rate of 2. Cracking of furnace pressure alarm control systems,
burning walls tubes and damper
3. Occurrences of 2. Review of current
backfire operating
procedures if high
pressure
occurrences are
frequent
Temperature 10B High 1. Too much fuel gas 1. Thermal creep of 1. Installation of 1. Regular
and air feed SMR tubes temperature inspections and
2. No reactant flow in 2. Furnace walls would indicator TI-202, maintenance of
SMR tubes crack TI-203 valve and control
2. Install control valve system
FCV-108

Production of Hydrogen via Syngas Route 10-22


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

10.3 PLANT LAYOUT

Plant layout is the spatial arrangement of items of process vessels and equipment and
their connection by pipes, ducts, conveyors or vehicular transportation, as defined by
Mecklenburgh [R2]. It is essential that plant layout is carefully thought out to satisfy the following
key considerations:

 Cost-effective use of space


 Risk-free and efficient construction
 Reliable, efficient and safe operations
 Ease of maintenance and repair of process and associated auxiliary units, carried out on
site or ex situ
 Minimal hazard and nuisance caused to the public

Besides safety and economic concerns, other factors such as process requirements, fire-fighting
and emergency capabilities, administrative and medical support infrastructure would also have to
be incorporated into the overall plant layout. An efficient transportation network within the plant
for the movement of materials, personnel and emergency services would also be needed. These
key issues would be duly covered in the following paragraphs.

10.3.1 Segregation

A main process area was designated, housing the primary process units such as the
furnace, SMR, HTS, LTS and the PSA unit. This facilitated the movement of material from one
process unit to the other and allowed for lower piping cost.

For safety and loss prevention, this main process area was deliberately sited away from
the main administrative building, laboratory and other buildings which house work personnel.
Furthermore, to control access to the main process area and also to the auxiliary units and waste
treatment area, a security fence was erected and an ‘official access only’ system was
implemented, in view of increasing security and intrusion concerns.

Production of Hydrogen via Syngas Route 10-23


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

A safety clearance of at least 60 m would also be needed between this main process area
and the main buildings where plant personnel are housed [R2].

10.3.2 Transportation Considerations

A rectangular grid was employed in the preliminary plant layout as it is often the most
cost-effective arrangement. This is because overhead piperacks, sewer systems, underground
piping systems, trenches, electric cables and instrument lines very often follow the road layout
[R2]
. Therefore, curved roads should generally be avoided to facilitate the laying of these lines and
systems.

Roads should also be built in such a way so as to allow easy access for emergency and
fire-fighting services. This can be accomplished with the use of a peripheral road system which
allows for at least 2 approaches to all major fire risks, e.g. the main process area. Roads in the
plant should also have access to the public road system at a minimum of 2 points. Moreover,
they should be sited at a reasonable distance from any process unit or building in order to
effectively carry out firefighting or administer emergency care. The actual distance is usually set
at around 18 to 45 m [R2].

The main perimeter road was set to be 10 m wide. This is to facilitate the bulk of daily
vehicular traffic. Primary and secondary access roads were designated to be 6 m and 3.5 m wide
respectively. Adequate parking space was also allocated for work personnel, visitors and
loading/unloading vehicles. These were sited away from wind-blown dusts and the main process
area for safety and security purposes, and suitably sized to prevent congestion during shift
changeover [R2].

10.3.3 Administration

Plant personnel with more general site responsibilities, e.g. human resource and IT
departments, should be sited in an administrative building located in a non-hazardous area away
from the main process units. This building should be sited upwind of possible fumes and

Production of Hydrogen via Syngas Route 10-24


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

emission from the process units, and near the main entrance to the plant to facilitate evacuation.
An estimated 50 administrative employees was used as the benchmark in this preliminary design,
hence according to Mecklenburgh [R2], an area of 500 m2 would suffice for preliminary layout
planning.

10.3.4 Laboratory

An onsite laboratory is critical in the setup of any plant as it provides a readily-available


source of analytical information on the quality of intermediates and products. This allows
engineers and operators to effect any changes to the process parameters in order to correct any
deviations. An estimated 20 laboratory staff would suffice for this preliminary design; hence an
area of 400 m2 would be used [R2].

10.3.5 Workshop

A workshop is needed for mechanical repairs and maintenance to be carried out onsite.
This will help to defray costs related to delays in repair and transport elsewhere. An estimate of
30 people would be used; hence an area of 600 m2 would be set aside for such a workshop [R2].

10.3.6 Control Room

The location of a control room is based on normal operating requirements and the need
for protection during emergency situations. Operators would be more inclined to be on the plant
should the control room be nearer to the plant. As a result, they would be more likely to observe
any malfunctions and plant deviations, hence preventing the occurrence of a serious fault.
Instrument cables would also be shortened if the control room is sited nearer the plant. It has also
been reported that at distances greater than 35 m and particularly over 100 m, operators will tend
not to go into the plant, especially in inclement weather [R2].

Nevertheless, the shorter the distance the control room is to the plant, the greater the need
for the room to be reinforced for personnel protection, and hence a higher cost is needed.

Production of Hydrogen via Syngas Route 10-25


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Therefore, a suitable distance of about 30 m between the control room and the main process area
was chosen in this design [R2]. An estimated area of 200 m2 was used for the control room.

10.3.7 Transformer Substation

The substation is usually sited at the edge of the plant, in areas of the lowest electrical
hazard rating. This will ensure a continuous electrical supply to the entire plant, critical to its
daily functioning.

10.3.8 Emergency Services

Emergency services such as ambulance and fire stations need to be given rapid access to
the entire site, without causing any hazard to the existing plant traffic. Preferably, they should be
housed outside the main fence but close to the main plant entrance. A 500 m2 area would be
recommended for this hydrogen plant.

An area adjacent to the main administrative building would also be set aside as an
emergency assembly area. This would help in the accounting of plant personnel should an
emergency incident arise.

10.3.9 Amenities (Medical Centre and Canteen)

The medical centre is essential in administering emergency and daily medical care to the
plant employees. Since it is frequently used by staff from all over the site, it should be located in
a central, non-hazardous area, preferably grouped together with other amenities such as the
canteen. This will help to cut down on time spent traveling to these amenities. Also, it should be
sited upwind from drifting fumes and noise from process units.

It was hence decided that an area of 30 m2 would be used for the medical centre, able to
cater to about 200 employees and contractors. An area of 200 m2 would be used in sizing the
canteen, also with the capacity to accommodate 200 personnel at one time [R2].

Production of Hydrogen via Syngas Route 10-26


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

10.3.10 Process and Auxiliary Units

10.3.10.1 Furnace (Housing SMR)

The foremost considerations in the location of a furnace are safety issues since it is a
constant source of ignition. Where practical, furnaces should be sited in upwind locations so that
flammable gases or vapors are less likely to be blown towards the furnace, resulting in ignition.
Furnace transfer lines should also be kept short, with a common stack policy being employed.
Hence, process equipment which is directly connected to the furnace should be sited as close as
possible, without compromising on the recommended safety distance of 30 m from any
equipment which could be possible sources of ignition.2 Also, underground drain-points and
manhole covers within 30 m of the furnace walls should be sealed, and pits or trenches should
generally be avoided from extending under furnaces.

With regards to the abovementioned considerations, the furnace housing the SMR would
be located within the designated main process area housing the other major units. The
recommended safety spacing would be a distance of 15 m between the furnace and the HTS and
LTS reactors, and a distance of 30 m between the furnace and the PSA unit, which is considered
to be a process unit with a low flash point due to the high concentration of H2 present [R2].

10.3.10.2 Reactors (HTS, LTS), PSA and Knockout Drum

HTS and LTS are typical fixed-bed reactors loaded with catalyst in bulk between
supports within the reactor vessel. The PSA unit also faces similar considerations due to its usage
of bulk catalyst as an absorbent; hence it was mentioned together in this section.

As catalysts have a fixed effective shelf life of a few years, provisions have to be made
for the removal and loading of catalysts. The units have to be sufficiently elevated from the
ground so as to allow catalyst removal by mechanical transport, belt conveyors, fluid conveying
or hand trucks. Clearance should be allowed for the usage of mechanical drills and other
equipment should coking, sintering, or hard agglomeration of the catalyst [R2].

Production of Hydrogen via Syngas Route 10-27


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

According to Mecklenburgh [R2], an area of 4 m2 must also be available at the base of


each reactor for the transport and temporary storage of fresh and spent catalyst.

It is also important to note that the PSA unit is used to concentrate the amount of H2.
With H2 being a vapor with a very low flash point of -273°C [R3], care would need to be exercised
in the safety distances needed. Since the PSA unit consists of 8 separate columns, it has been
recommended that such process equipment with low flash points should be spaced 2 m away
from one another [R2]. Also, it would be housed together in the main process area, at a distance of
at least 5 m from the HTS and LTS reactors, and a distance of at least 30 m from the furnace.
The knockout drum would be sited just next to the LTS unit.

10.3.10.3 Cooling Tower

Problems associated with the location of a cooling tower are often related to the large
volumes of very humid air which emanates from it, compounding the already high levels of
humidity normally experienced in Singapore. The moisture can lead to fog, precipitation and
corrosion issues in areas downwind of it [R2].

Towers should also be sited to mitigate the effects of wind drift on roads, rail, plant and
the neighborhood of the site. It is important to check that any possible corrosive emissions from
the vents of the HTS and LTS reactors, and the stack emissions from the furnace, would not be
entrained within the cooling tower.

Specifically for our project, a mechanical-draught tower was used. These require power
and may generate associated fan noise. If the entire plant was sited near a residential area, a
slower fan speed should be employed. Alternatively, buildings or sound screens could be erected
between the tower and the residential area.

Hence, the cooling tower has been separately sited far away from the main process area,
i.e. as an offsite facility, so as to prevent any entrainment of corrosive vapors.

Production of Hydrogen via Syngas Route 10-28


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

It has been accorded a safety distance of at least 30 m from the process area, at least 60 m
from administrative buildings, at least 30 m from the fire station and at last 45 m from the main
plant substation [R4].

10.3.10.4 Heat Exchangers

Heat exchangers should be located within the conventional process unit plot area, in close
proximity to the equipment which they are associated with. This would minimize the cost of pipe
runs and also facilitate operator and maintenance access. Heat exchangers between two process
equipment which are far away should be sited at optimal points in relationship to pipe tracks [R2].
However, due to the close proximity of our major process units to one another, with the
exception of the cooling tower, it would not be a major issue for consideration in this preliminary
design.

If exchangers are located in pairs, or in larger groups, they can be stacked on top of one
another. A spacing of 0.45 m (18 inch) should be provided to allow maintenance to be carried
out on the flange bolts easily [R4]. By this means, there could be resultant savings on service
pipework, pipebridge and structural work etc [R2]. However, process piping and access steel work
may actually increase consequently; therefore a compromise has to be made. Generally, most
exchangers would also be placed on a base about 1 m above ground level for the provision of
drain connections.

As there are no restrictions on minimum safety clearances between heat exchangers and
the specific process units that are found in our preliminary design, it would be considered that
they occupy the space in between the safety clearances of the process units.

10.3.10.5 Flares

Flares are used to burn away excess gases in an emergency situation and also to flare
away off-specification gases such as H2. A sterile radius of at least 60 m should be maintained

Production of Hydrogen via Syngas Route 10-29


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

around the flare, with only associated flare equipment and access roads allowed within this
radius. Also, the flare stacks should be located downwind from the main process areas and at
least 100 m away to provide for the dispersion of vapor releases [R2].

10.3.10.6 Wastewater Treatment Plant

A wastewater treatment plant is also needed to treat the condensate from the knockout
drum, the blowdown from the cooling water tower and any other liquid plant effluent before it is
discharged. It is usually sited at the perimeter of the site.

The estimated total effluent from the knockout drum and the cooling water tower is
around 873760 m3/year, assuming 8000 operating hours in a year. Comparing this with a water
treatment plant sited in Changi, Singapore5, which processes 292 million m3 of wastewater per
year (calculated from a daily rate of 800000 m3/day) and occupies an area of 55 ha (550000 m2),
the area needed for the onsite treatment plant would be estimated to be around 1650 m2.

Base Area Base Area


Process & Auxiliary Units Plant Facilities
(m2) (m2)
Furnace (housing SMR) 891 Administrative Building 500
HTS 9.4 Laboratory 400
LTS 8.6 Workshop 600
Knockout Drum 3.0 Control Room 200
PSA 144 Transformer Substation 160
Cooling Water Tower 733 Fire Station 500
Flare 25 Medical Centre 30
Wastewater Treatment Plant 1650 Canteen 200
Table 10-11: Base areas of process, auxiliary and other plant facilities

From Figure 10-1, the plant area was estimated to be around 29400 m2.

Production of Hydrogen via Syngas Route 10-30


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Fig 10-1: Plant layout

10.4 OCCUPATIONAL SAFETY

10.4.1 Personal Protection Equipment (PPE)

The safety requirements for different tasks in different parts of the plant are different.
Thus it is important to consult the Safety, Health and Environment department to ensure that the
correct PPE are worn [R1] when performing each task.

Production of Hydrogen via Syngas Route 10-31


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

Personal protection equipment is extremely important in preventing or reducing exposure


by providing a barrier between the worker and the workplace environment. This is for the benefit
of workers’ safety and health. However, by itself, it does not prevent accidents. It is only acting
as a secondary measure for safety and health purposes.

One of the most important equipment for this plant would be self-contained breathing
apparatus. This is because the dangers of this plant would mostly be caused by inhalation.
Therefore, this equipment has to be strategically placed in areas where leaks might occur,
especially in confined spaces. Other equipment needed would be safety glasses, safety gloves
and safety shoes.

Employers have to identify and provide the appropriate PPE for their employees. They
would also have to train employees in using and caring for the PPE. Periodically, they should
also review and check the PPE, replace worn out items and make the PPE program more
effective.

Employees should properly adhere to the regulations on wearing their PPE. They should
also attend training sessions for the use of their PPE. They should have the responsibility to take
care and maintain their PPE and inform their superiors if there is a need to replace these items.

10.4.2 Noise

Noise [R1] problems are commonplace in chemical plants. They are measured in decibels
(dB). According to regulations, noise levels should not exceed 85dB for an 8 hour workday.
Measures must be taken if the exposed noise level is higher than 85dB. Control of the noise can
happen at either the source or the receiver of the noise. At the source of noise, one can either
enclose the source using shields such as plywood or noise absorbing foams. It is also possible to
employ sound barriers to reduce the noise level transmitted to workers. Otherwise, at the receiver
level, ear plugs and ear muffs are the most commonly used PPE for regulating exposure to noise.

Production of Hydrogen via Syngas Route 10-32


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

10.4.3 Ventilation

Ventilation [R1] is extremely important for this plant for the following reasons:

 It can remove dangerous concentrations of flammable and toxic materials

 It can be highly localized, reducing the quantity of air moved

 Ventilation equipment is readily available and can be easily installed

 It can be added to an existing facility

However, the major disadvantage is operating cost, which is rather prohibitive.


Ventilation systems comprise of fans and ducts that effectively dilute the contamination using
dilution ventilation. Fresh air is flowed in large amounts to dilute the contamination. Workers
would still be exposed to the contaminants, but in lesser concentrations.

Production of Hydrogen via Syngas Route 10-33


CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

10.5 OCCUPATIONAL HEALTH HAZARD IDENTIFICATION

It is important to identify any safety hazards brought about by the chemical nature of the reactants and products present in the
steam methane reformer. A good knowledge of the nature of these components is necessary for operators to know how to react to
exposure to these components.

Table 10-12: Summary of nature and associated hazards of chemicals [R6]


Chemical Threshold Lower Personal Health Effects
Limit Exposure Protective Acute Chronic
Value Limit and Equipment
(TLV) Upper (PPE)
Exposure
Limit (LEL
– UEL)
Methane N.A. 5 – 15% Safety glasses Simple asphyxiant- reduces the amount of oxygen in the N.A.
and/or face air. Exposure to oxygen-deficient atmospheres (less than
shields 19.5 %) may produce dizziness, nausea, vomiting, loss of
consciousness, and death. At very low oxygen
concentrations (less than 12 %) unconsciousness and
death may occur without warning. It should be noted that
before suffocation could occur, the lower flammable limit
for Methane in air will be exceeded; causing both an
oxygen deficient and an explosive atmosphere.
CO 25 ppm 12.5 – 74% Safety glasses, Inhaled carbon monoxide binds with blood hemoglobin to N.A.
TWA safety gloves, form carboxyhemoglobin. Carboxyhemoglobin cannot
safety shoes, and take part in normal oxygen transport, greatly reducing the
self-contained blood’s ability to transport oxygen. Depending on levels

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Team 32 Safety, Health & Environment (S.H.E.)

breathing and duration of exposure, symptoms may include


apparatus during headache, dizziness, heart palpitations, weakness,
emergency confusion, nausea, and even convulsions, eventual
unconsciousness and death.
H2 N.A 4% - 74.5% Wear chemical Nausea, vomiting, difficulty breathing, irregular heartbeat, N.A
resistant gloves headache, fatigue, dizziness, disorientation, mood swings,
tingling sensation, loss of coordination, suffocation,
convulsions, unconsciousness, coma
CO2 5000 ppm Non- Safety glasses, Carbon dioxide is a cerebral vasodilator. Inhaling large N.A
TWA flammable safety gloves, quantities causes rapid circulatory insufficiency leading to
safety shoes, and coma and death. Asphyxiation is likely to occur before the
self-contained effects of carbon dioxide overexposure. Low
breathing concentrations cause increased respiration and headache.
apparatus during Product is a simple asphyxiant. Effects of oxygen
emergency deficiency may include any, all or none of the following:
rapid breathing, diminished mental alertness, impaired
muscle coordination, blurred speech, and fatigue.
As asphyxiation progresses; nausea, vomiting, and loss of
consciousness may occur, eventually leading to
convulsions, coma and death.

These are the procedures to be taken for spills, fire-fighting and medical aid.

Table 10-13: Summary of safety, fire-fighting and medical aid measures [R6]
Chemical Spill/leak measures Fire-fighting measures Medical Aid measures
Methane Personal precautions: Wear self Extremely flammable. Exposure to fire Inhalation: Remove victim to
contained breathing apparatus when may cause containers to uncontaminated area wearing self-
entering area unless atmosphere is rupture/explode. If possible, stop flow contained breathing apparatus.
proved to be safe. Evacuate area. Ensure of product. Move away from the Keep victim warm and rested. Call
adequate air ventilation. Eliminate container and cool with water from a a doctor. Apply artificial

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Team 32 Safety, Health & Environment (S.H.E.)

ignition sources. protected position. Do not extinguish a respiration if breathing stopped.


Environmental precautions: Try to stop leaking gas flame unless absolutely Ingestion: Ingestion is not
release. necessary. Spontaneous explosive re- considered a potential route of
Clean up methods: Ventilate the area. ignition may occur. Extinguish any exposure.
other fire. In confined space, fire
fighters must use self-contained
breathing apparatus.

CO Personal precautions: Evacuate area. Extremely flammable. Exposure to fire Inhalation: Remove victim to
Eliminate ignition sources. Use self- may cause containers to uncontaminated area wearing self-
contained breathing apparatus and rupture/explode. If possible, stop flow contained breathing apparatus.
chemically protective clothing. Ensure of product. Move away from the Keep victim warm and rested. Call
adequate air ventilation. Wear self container and cool with water from a a doctor. Apply artificial
contained breathing apparatus when protected position. Do not extinguish a respiration if breathing stopped.
entering area unless atmosphere is leaking gas flame unless absolutely Ingestion: Ingestion is not
proved to be safe. necessary. Spontaneous explosive re- considered a potential route of
Environmental precautions: Try to stop ignition may occur. Extinguish any exposure.
release. other fire. Fire fighters must use self-
Clean up methods: Ventilate the area. contained breathing apparatus.
H2 Evacuate all personnel from affected If possible, stop the flow of hydrogen. Inhalation: Remove victim to
area. Use appropriate protective Cool surrounding containers with uncontaminated area wearing self-
equipment. If leak is in user’s water spray. Hydrogen burns with an contained breathing apparatus.
equipment, be certain to purge piping almost invisible flame of relatively Keep victim warm and rested. Call
with an inert gas before attempting low thermal radiation. Hydrogen is a doctor. Apply artificial
repairs. If leak is in the container of very light and rises very rapidly in air. respiration if breathing stopped.
container valve, contact closest supplier Should a hydrogen fire be Ingestion: Ingestion is not
location. extinguished and the flow of gas considered a potential route of
continue, increase ventilation to exposure.
prevent an explosion hazard,
particularly in the upper portions.
CO2 Personal precautions: Evacuate area. Non-flammable. If possible stop flow Inhalation: Remove victim to

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Team 32 Safety, Health & Environment (S.H.E.)

Wear self contained breathing apparatus of product. Move away from the uncontaminated area wearing self-
when entering the area unless container and cool with water from a contained breathing apparatus.
atmosphere is proved to be safe. Ensure protected position. In confined space, Keep victim warm and rested. Call
adequate air ventilation. fire-fighters must use self contained a doctor. Apply artificial
Environmental precautions: Try to stop breathing apparatus. respiration if breathing stopped.
release. Prevent from entering sewers, Skin/eye contact: Immediately
basements and workpits, or any place flush eyes thoroughly with water
where its accumulation can be for at least 15 minutes. In case of
dangerous. frostbite, spray with water for at
Clean up methods: Ventilate the area. least 15 minutes. Apply a sterile
dressing. Obtain medical
assistance.
Ingestion: Ingestion is not
considered a potential route of
exposure.

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CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

10.6 ENVIRONMENTAL IMPACT ASSESSMENT

Environmental impact assessment (EIA) refers to the need to identify and predict the
impact on the environment and on man’s health and well-being of legislative proposals, policies,
programmes, projects and operational procedures, and to interpret and communicate information
about the impacts [R7]. Although there is no legal requirement for EIA to be carried out for
projects in Singapore [R8], an EIA would be carried out in this preliminary design of a hydrogen
plant so as to address the environmental aspects of undertaking the operation of a hydrogen plant.

10.6.1 Objectives

The primary objectives of an EIA are summarized as follows [R9]:

 To determine methods to prevent or mitigate environmental damage


 To mitigate environmental damage through the application of practical meditative actions
 To make known to the public and the public or private bodies in charge of the project the
noteworthy environmental effects of such an undertaking
 To make known to the public justifications of governmental approvals of undertaking
with substantial environmental effects
 To encourage cross-agency interaction in the assessment of projects
 To engage the public in the planning process

10.6.2 Risk Assessment Matrix

In order to assess the environmental impact of the daily activities of the hydrogen plant
and its accompanying wastewater treatment plant, a risk assessment matrix as shown in Table
10-14 was utilized to summarize the offending activities and its associated impacts on the
environment and work personnel. Criteria employed in this risk assessment matrix are reflected
in the accompanying legend, with risk ranking (RR) having considered the overall consequences
(OC) and the likelihood of occurrence (LH). The RR would serve as a clear indication of the risk
level of a particular activity in the operation of the hydrogen plant.

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Team 32 Safety, Health & Environment (S.H.E.)

Table 10-14: Risk assessment matrix detailing the environmental impact of hydrogen plant operations
Activity/
Process/ Aspect/Associated Mitigation
N/A/E Impact/Effect P PD ENV REP OC LH RR
Product/ Hazard Measures
Services
Flaring 1. Complete N 1. Increased IV IV III YES IV A M 1. Reduce
combustion yields greenhouse frequency of
CO2, a major effect excess waste
greenhouse gas gas emission,
emergency
2. Incomplete N 1. Increased III III II YES III B M flaring and
combustion yields greenhouse off-spec
methane (from effect flaring
natural gas), H2 2. Emission of incidents
(off-spec product), H2, a highly 2. Try to achieve
soot and CO flammable absolute
gas and an combustion
explosive through use of
hazard excess air
3. Soot can 3. Flare got
worsen to opacity
regional haze analyzer
problem 4. Installation of
4. CO can air scrubbers
indirectly 5. Periodic
raise monitoring to
methane and prevent
tropospheric excessive
ozone, which emissions
also
contribute to

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Team 32 Safety, Health & Environment (S.H.E.)

the global
warming

Emission 1. Emission of N 1. Increased IV IV III YES IV A M 1. Ensure


of stack greenhouse gases greenhouse efficient
gases such as CO2 effect furnace
during operation,
furnace using the
operation least possible
fuel gas
2. Emission of NOx N 1. Acid rain III III II YES II A H 1. Install
due to high formation temperature
temperature in sensor to
furnace radiant monitor
section radiant
section
temperature
2. Install NOx
controller

3. Emission of soot N 1. Soot can III III II YES III B M 1. Install opacity
and CO due to contribute to analyzer to
incomplete regional haze detect
combustion problem excessive soot
2. Emission of formation
CO can 2. Ensure excess
indirectly air is present

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Team 32 Safety, Health & Environment (S.H.E.)

raise to minimize
methane and incomplete
tropospheric combustion
ozone,
which also
contribute to
the global
warming
4. If sulfur is found A 1. Acid rain III III II NO III D L 1. Use fuel gas
in natural gas formation feed with
feed, SO2 could less sulfur
be released
Vapor 1. Emission of A 1. Increased II II III NO II C M 1. Isolation and
leakages methane, greenhouse repair of
from hydrogen, CO and effect due to leaking pipes
pipelines CO2 methane, CO 2. Conduct
and CO2, regular checks
leading to
global
warming
2. Emission of
H2, a highly
flammable
gas and an
explosive
hazard
3. Exposure to
CO, an
asphyxiant,
can result in
dizziness,

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Team 32 Safety, Health & Environment (S.H.E.)

nausea,
vomiting,
loss of
consciousnes
s and death

2. Hot steam A 1. Injury to III IV IV YES IV C L 1. Conduct


emissions due to work steam leak
ruptured pipe personnel test
2. Clamp and
repair leaking
pipes
Storage of 1. Leakage of non- A 1. Soil III IV I YES III C M 1. Set storage
cooling volatile chemicals contaminatio limits
water n 2. Ensure proper
chemicals 2. Water storage of
(biocides, contaminatio chemicals
corrosion n 3. Containment
inhibitor) of leaks
4. Neutralization
or dilution
methods
5. Proper
disposal of
expired
chemicals
6. Regular checks
by cooling
tower unit

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Team 32 Safety, Health & Environment (S.H.E.)

operators
7. Periodic soil
quality tests
Knockout 3. Condensate A 1. Soil III IV I YES III C M 1. Containment
drum leakage from contaminatio of leaks
operation drum and n 2. Regular
associated 2. Water pipeline
pipelines, carrying contaminatio checks
dissolved n 3. Periodic
hydrocarbons and maintenance of
carboxylic acids) drum and
pipelines
Cooling 1. Water droplets or A 1. Legionnaire II IV III YES III C M 1. Periodic
tower water mist aerosol ’s Disease disinfection of
operation generated as drift can be cooling tower
transmitted, using chlorine
[R11]
leading to
pneumonia 2. Installation of
in serious drift
cases [R10] eliminators
3. Usage of
biocides to
prevent
accumulation
of algae and
scaling
2. Discharge of A 1. Raise III IV I YES III D L 1. Ensure cooling
heated cooling temperature water is not
water into s of directly
surrounding water surrounding discharged into
bodies water surrounding

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Team 32 Safety, Health & Environment (S.H.E.)

bodies, water bodies


decreasing 2. Installation of
amount of temperature
dissolved sensors at
oxygen discharge outlet
Waste 1. Discharge of N 1. Water III IV IV YES IV A M 2. Installation of
water treated effluent pollution sensors for
treatment detection of
elevated levels
of chemical
release
3. Monitor pH
levels

Catalyst 1. Metal content N 1. Soil III IV II NO III C M 1. Proper disposal


change present in catalyst contaminatio of spent
out in n by metals catalyst
reactors 2. Water
and PSA contaminatio
unit n by metals

2. Dust particles N 1. Affects III IV III NO III C M 1. Don respiratory


from catalyst fines respiratory masks during
system of catalyst change
work out operation
personnel

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Team 32 Safety, Health & Environment (S.H.E.)

Legend for Table 10-14


Symbol Description
N/E/A Normal Operation / Emergency / Abnormal Operation
P Injury to People
PD Property Damage
ENV Environmental Impact
REP Repetitive
OC Overall Consequences
LH Likelihood of Occurrence
RR Risk Ranking

Probability Category Definition Probability


A Possibility of repeated incidents A B C D E
B Possibility of isolated incidents I
C Possibility of occurring sometimes II
D Not likely to occur III
E Practically impossible IV

Considerations
Consequence Category Property
Health/Safety Environmental Impact
Damage
Large
I Fatalities / serious impact on public Major/Extended duration/Full scale response
community
Serious injury to personnel / limited Small
II Serious/Significant resource commitment
impact on public community
Medical treatment for personnel /
III Minor Moderate/Limited response or short duration
No impact on public
Minimal to
IV Minor impact on personnel Minor/Little or no response needed
none

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CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

10.6.3 Elements of Environmental Impact Assessment

10.6.3.1 Gaseous emissions

The air pollution caused by the H2 plant may include greenhouse gases such as carbon
dioxide, methane and NOx, hazardous gases such as carbon monoxide and sulphur dioxide, and
also flammable gases such as hydrogen. These gases could cause much harm to the environment,
for example, global warming due to greenhouse gases, acid rain due to acidic gases, ozone
depletion, and even fires and explosion caused by flammable gases. Some of these gases also can
cause health problems in people who are exposed to it without proper protection. Sulphur
dioxide, nitrogen dioxide and ozone in the lower atmosphere can cause respiratory diseases in
people. Emission limits of sulphur dioxide are 500mg/Nm3, and that of nitrogen dioxide are
700mg/Nm3.

Carbon monoxide is also dangerous and can cause death through asphyxiation in
excessive doses. Emission limits of carbon monoxide are 625mg/Nm3. During changeout of
catalyst, it could cause the broken, fine metal catalysts to emit into the air as respirable
suspended particles (PM10). PM10 refer to particulate matter of size 10mm and below. These
particles have health implications as they are able to penetrate into the deeper regions of the
respiratory tract. In very large amounts, the particles cause breathing and respiratory problems,
and aggravate existing respiratory and cardiovascular diseases. Hence, to reduce the emissions of
these vapours, mitigation measures as mentioned in Table 10-14 is essential to be adhered to.

10.6.3.2 Effluent discharge

The Pollution Control Department in Singapore regularly monitors water quality of


various inland water bodies and coastal areas. For this hydrogen plant, the effluent would come
from the cooling tower water and chemicals as well as the wastewater from the knockout drum
which comprises of hydrocarbons. The table below shows the allowable limits for trade effluent
discharged into a public sewer/watercourse/controlled watercourse.

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Team 32 Safety, Health & Environment (S.H.E.)

Public Sewer Watercourse Controlled


Items of Analysis watercourse
Units in milligram per litre or otherwise stated
1. Temperature of discharge 45oC 45oC 45oC
2. BOD (5 days at 20oC) 400 50 20
3. COD 600 100 60
4. Hydrocarbon 60 10 -
5. Total Suspended solids 400 50 30
Table 10-15: Allowable limits for trade effluent discharge

Where, Biochemical Oxygen Demand (BOD) and Chemical Oxygen Demand (COD) are
used as wastewater quality indicators. There would be fees levied for trade effluent with BOD in
excess of 400mg/l to 4000mg/l. For BOD exceeding 4000mg/l, the trade effluent would have to
be treated to below 4000mg/l before discharging into public sewers. Effluent discharge has to be
treated to meet these limits before discharge.

10.6.3.3 Waste management & minimization

Waste management to be considered for this hydrogen plant would be the disposal of the
spent metal catalysts after catalyst changeout. Licensed general waste collectors will be
employed for this task. It is an offence for any person or company to collect or transport waste as
a business without a valid General Waste Collector License. The spent catalyst has to be
carefully handled, especially because catalyst fines might get into the air and cause health
problems to the people.

10.6.3.4 Energy efficiency

The National Energy Efficiency Committee (NEEC) is a committee with 3P (People,


Private, and Public Sector) representation. It seeks to integrate the promotion of energy
efficiency and the use of clean energy sources with the reduction of emissions of air pollutants
and carbon dioxide from the production of energy. The key objectives of the NEEC are as
follows:

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Team 32 Safety, Health & Environment (S.H.E.)

• Promotion of energy conservation through efficient use of energy in the industrial,


building, and transportation sectors
• Promotion of the use of cleaner energy sources such as natural gas and renewable energy
sources
• Promotion of Singapore as a location for the pilot test-bedding of pioneering energy
technologies and as the hub for development and commercialization of clean energy
technologies

As can be seen from our mitigation measures, we are actively fulfilling the above mentioned
objectives of the NEEC.

10.6.4 Hydrogen Product Life Cycle Assessment

Fig 10-2: Hydrogen life cycle

Life cycle assessment (LCA) is defined as a systematic analytical method that helps
identify and evaluate the environmental impacts of a specific process or competing processes
[R12]
. To quantitatively account for its impact on the environment, material and energy balances

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CN 4120: Design II
Team 32 Safety, Health & Environment (S.H.E.)

are performed in a “cradle-to-grave” manner on the processes required to turn raw feedstock into
tangible products. Possible emissions, resource consumption and net energy consumption would
serve as primary indicators for the efficiency of the hydrogen life cycle. Finally, this LCA will be
used as the basis of comparison with other hydrogen generation methods to weigh the
environmental benefits and disadvantages of these various methods.

A study done by the National Renewable Energy Laboratory [R12], under the U.S.
Department of Energy, indicated that CO2 was emitted in the greatest amount, making up 99%
by weight of the total air emissions during steam methane reforming. This amount of CO2 also
contributed for 89.3% of the system’s global warming potential (GWP), defined as a
combination of CO2, CH4, and N2O emissions expressed as CO2-equivalence for a 100 year time
frame. Moreover, methane accounted for 10.6% of the GWP. Overall, the hydrogen plant itself
contributed 74.8% of the greenhouse gas emissions. Besides these gases, other hydrocarbons
(C2+), NOx, SOx, CO, particulates and benzene make up the remainder of the emissions. These
usually came about from natural gas production and distribution. Water was also consumed in
copious amounts in the hydrogen plant in the SMR, HTS and LTS reactors.

In terms of energy balance, it was determined that a major component of energy


consumption was found contained in the natural gas feedstock. On a life cycle basis, for every
MJ of fossil fuel consumed by the system, 0.66 MJ of hydrogen are produced on a LHV basis.
This figure has also included the energy used in the production, distribution of natural gas, and in
the generation of electricity to power the hydrogen plant itself [R12].

10.6.4.1 Ramifications of Hydrogen LCA

Hydrogen, an energy carrier, is perceived by engineers and scientists to be the energy


system for the 21st century. This is due to its abundance in the universe. However, H2 does not
exist naturally on Earth. It is mainly found on Earth as water and in organic compounds such as
methane, coal, petroleum and biomass.

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Team 32 Safety, Health & Environment (S.H.E.)

At present, the majority of hydrogen is produced by the steam methane reforming method,
since it is still the most economical choice. However, this process relies heavily on liquid or gas
hydrocarbon fuels as the basic material for manufacture and as energy input for its production.
Therefore, the associated environmental impact is significant, as greenhouse gases such as CO2
and NOx would be emitted.

Moreover, another inherent problem in the product life cycle of hydrogen is related to the
lower energy density per unit volume of hydrogen. Hence, for hydrogen to be used as
transportation fuel, an energy-intensive liquefaction process is required. This not only incurs
additional cost, but also contributes to the emission of greenhouse gases, leading to increased
global warming.

Hence, although hydrogen is indeed a promising candidate as a future energy carrier,


with its reputation as a clean fuel with zero toxic emissions, the overall life cycle efficiency at
present is negative (-39.6%), i.e. the energy in the natural gas is greater than the energy content
of the hydrogen produced. It has also been mentioned above that for every MJ of fossil fuel
consumed by the system, 0.66 MJ of hydrogen are produced (LHV basis). 12 Therefore, unless
higher life cycle efficiencies are attained, the amount of resources, emissions, wastes and energy
consumption would remain a stumbling block towards its widespread implementation. Most
importantly, its adverse effect on the environment would still remain an issue to be resolved.

10.7 CONCLUSION

To conclude, it is an undeniable fact that safety issues should take precedence ahead of
economic considerations in the area of plant design and operation. The safe running of the
hydrogen plant will not only minimize human casualties and environmental harm, but can also
work hand-in-hand to meet economic demands being placed on the plant.

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Team 32 Safety, Health & Environment (S.H.E.)

REFERENCES

[R1] : Daniel, A.C. & Louvar, J.F. (2002). Chemical Process Safety: Fundamentals with
Applications. 2nd Ed., Upper Saddle River, NJ: Prentice Hall.
[R2] : Mecklenburgh, J. C. (1985). Process Plant Layout, London: G. Godwin.
[R3] : Hydrogen Properties. Retrieved April 12, 2008, from U.S. Department of Energy Web
site: http://www1.eere.energy.gov/hydrogenandfuelcells/tech_validation/pdfs/fcm01r0.pdf
[R4] : Bausbacher, E. & Hunt, R. (1993). Process Plant Layout and Piping Design, New Jersey:
Prentice-Hall.
[R5] : Changi Water Reclamation Plant. Retrieved April 13, 2008, from CPG Corporation Web
site: http://www.cpgcorp.com.sg/portfolio/viewdetails.asp?Lang=EN&PCID=11&PDID=163
[R6] : Physical properties of gases, safety, MSDS, enthalpy, material compatibility, gas liquid
equilibrium. Retrieved April 14, 2008 from Air Liquide Web site:
http://encyclopedia.airliquide.com/encyclopedia.asp?CountryID=19&LanguageID=11
[R7] : Munn, R.E. (1979). Environmental Impact Assessment: Principles And Procedures. 2nd
Edition. New York: Wiley.
[R8] : Briffett, C. (1994). The Effectiveness of Environmental Impact Assessment in Southeast
Asia.
[R9] : Bass, R.E., Herson, A.I. and Bogdan, K.M. (1999) CEQA Deskbook: A Step-by-step Guide
on how to Comply with the California Environmental Quality Act. 2nd edn., Point Arena, CA:
Solano Press.
[R10] : OSH Answers: Legionnaire’s Disease. Retrieved on April 16, 2008 from Canadian
Centre for Occupational Health and Safety Web site:
http://www.ccohs.ca/oshanswers/diseases/legion.html
[R11] : Legionnaire’s Disease eTool : Source and Control – Cooling Towers, Evaporative
Condensers and Fluids Coolers. Retrieved on April 16, 2008 from U.S. Department of Labor
Occupational Safety & Health Administration Web site:
http://www.osha.gov/dts/osta/otm/legionnaires/cool_evap.html#Treatment

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[R12] : Life Cycle Assessment Of Hydrogen Production Via Natural Gas Steam Reforming.
Retrieved on April 16, 2008 from National Renewable Energy Laboratory Web site:
http://www.nrel.gov/docs/fy01osti/27637.pdf

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Chapter 11 : INSTRUMETNATION & CONTROL

11.1 INTRODUCTION

Instrumentation and control of the plant is critical to the plant’s operation and product
quality. It helps to manage the product quality through proper control of the plant. The objectives
of instrumentation and control are based on two major aspects [R1]:
Safety, Health and Environment (SHE) – A safe plant operation prolongs the life of the
expensive equipment and protects the health of the operators. Safe and smooth plant operation is
achieved with proper control that will detect abnormalities and effect the corrective actions to
maintain the process variable within the permissible limits. In addition, safe operation keeps the
surrounding environment in check by preventing unexpected harmful emissions to the
atmosphere.
Product quality – Through control and instrumentation, the plant would be able to respond to
changes in operating conditions quickly and effectively, thus ensuring minimal disturbances to
the plant. Therefore, the production scheme remains unperturbed and generates products of
constant quality and yield.

The protection scheme of the safety design is shown:

Fig 11-1: Typical layers of protection in a modern chemical plant

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CN 4120: Design II
Team 32 Instrumentation & Control

This chapter looks at the process control system of the steam methane reformer (SMR).
The control and instrumentation of this section is fully developed by our team and will be
explained in detail. The installation of critical alarms and automatic safety lock systems to
protect property and employees during emergencies are also explored. The controls are
employed bearing in mind that non-essential controls were reduced to minimize cost of the
process control system, without compromising on safety and quality of products.

11.2 PROCESS CONSIDERATION AND DESCRIPTION

Aims and objectives

The furnace and SMR reactor are two important units to the plant. The steam methane
reformer generates hydrogen while the furnace controls the SMR process. Controlling the steam
methane reforming process ensures constant yield and profitability of the plant. It also prevents
any possible runaway reactions. As the SMR process is endothermic, the heat duty is supplied by
the furnace and hence combustion is strictly controlled to maintain constant reaction temperature.
In addition, the high temperature and pressure associated with furnace operations creates more
necessity to impose proper control on the furnace. The lack of control of process variables within
the furnace may pose environmental and safety issues. The important process parameters related
to these two units are listed below:

Important process variables of Furnace


1. Temperature
2. Pressure

Important process variables of SMR reactor


1. Temperature
2. Steam methane ratio

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Team 32 Instrumentation & Control

11.3 PROCESS CONTROL METHODOLOGY

The following steps will be used in the formulation of our instrumentation and control design.
1. Identify the variables to be controlled, measured and manipulated

2. Select the control strategy and structure

3. State the controller settings

The general control strategies are feedback and feed-forward control. Feedback control
provides an easy control of variables without extensive knowledge of the process. Feed-forward
control provides a safer control as compared to feedback control because it allows corrective
action to be taken before the process variables go out of hand. The advantages and disadvantages
of feedback and feed-forward control are summarized in Table 11-1:

Advantages Disadvantages
Feedback • Little knowledge is required • Poor control occurs if
of the control process time lags are significant

• Disturbance need not be • Closed-loop instability


measured may occur

• Corrective action will be • Process upset takes place


taken regardless of the before corrective action
source and type of is taken
disturbances

Feed-forward • Corrective action is taken • In depth knowledge of


before process upset occurs the process is required

• “Perfect” control can be • Ideal controllers may not


achieved. be present to effect
perfect control

Table 11-1: Summary of advantages and disadvantages of feedback and feed-forward control

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Team 32 Instrumentation & Control

11.4 SELECTION OF CONTROLLED, MANIPULATED AND MEASURED VARIABLE

A good control system can be achieved if the appropriate controlled and manipulated
variables are chosen. These are some guidelines we followed when selecting the variables [R1].

For controlled variable:


1. All variables that are not self-regulating must be controlled

2. Choose output variables that must be kept within equipment and operating constraints

3. Select output variables that represent a direct measure of product quality or that strongly
affect it

4. Choose output variables that interact with other controlled variables

5. Choose output variables that have favourable dynamic and static characteristics

For manipulated variable:


1. Select inputs that have large effects on controlled variables

2. Choose inputs that rapidly affect the controlled variables

3. The manipulated variables should affect the controlled variables directly rather than
indirectly

4. Avoid recycling of disturbances

For measured variable:


1. Reliable, accurate measurements are essential for good control

2. Select measurement points that have an adequate degree of sensitivity

3. Select measurement points that minimize time delays and time constraints

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Team 32 Instrumentation & Control

In our design, the major variables affecting the overall safety of the furnace are identified
as follows:

1. Pressure

Pressure control within the furnace is essential because it can compromise the
performance. Pressure drop within the reformer tubes has to be kept to a minimum for
favourable reaction conversion. Backflow within pipelines has to be avoided as well.
2. Temperature

Temperature control is essential to ensure that the reaction within the reformer tubes
proceed smoothly. It is also important to ensure that the materials of construction remain
intact by ensuring that the temperature within the furnace is kept below the creep
temperature of the materials. Flue gas temperature has to be controlled to prevent acid
gas condensation and to comply with governmental regulation.
3. Composition and Flow

The steam/methane ratio has to be kept above a minimum to prevent coking and high
pressure drop within the tubes. In addition, the air-to-fuel ratio into the furnace has to be
kept constant to ensure absolute combustion and maximum efficiency.

11.5 DETAILED CONTROL DESIGN FOR REFORMER FEED

11.5.1 Steam-to-Methane Ratio Control

One important control parameter in steam-methane reforming is the steam-to-methane


ratio. A low ratio is undesirable as it promotes the side reaction of coke formation on the catalyst,
which deactivates it and requires expensive replacement. Nonetheless, a high steam-to-methane
ratio will result in better conversion, but at the expense of elevated operating costs due to the
high cost associated with superheated steam. Hence, a compromise between methane conversion
and operating expense has to be made and in industries, this ratio is typically kept at 3:1.

Production of Hydrogen via Syngas Route 11-5


CN 4120: Design II
Team 32 Instrumentation & Control

Fig 11-2: Control scheme for steam/methane ratio control

To achieve this, a ratio control depicted in Fig 10-2 is employed to maintain the ratio
between steam and methane at 3:1 as stated in our design problem. The flow rate of the natural
gas stream is measured and transmitted by FT-101 to the ratio station FY-101. At the ratio
station, this signal is multiplied by an adjustable gain whose value is the desired ratio. The output
signal from the ratio station is then used as the set-point for flow controller FIC-102. This feed-
forward controller then adjusts the flow rate of the imported superheated steam by manipulating
the opening of the diaphragm valve FCV-102 using pneumatic signals.
In the preliminary design of this ratio control, it is assumed that molar flow rate is equal to the
volumetric flow rate which implies that possible pressure and temperature fluctuations in process
streams are not compensated.

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CN 4120: Design II
Team 32 Instrumentation & Control

11.5.2 Pressure Control Loop for Expander

A feedback control loop is used for all the expanders in the plant. The controlled variable
is the outlet pressure of the expanded vapour, while the manipulated variable is the inlet pressure
to the expander.

Fig 11-3: Control scheme for pressure control of expander discharge

The pressure transmitter (PT) would detect any deviations from the set point and send a
signal to the pressure controller (PIC) so as to adjust the valve which changes the inlet pressure
to the expander. This would then serve to bring the controlled variable back to its set point.

11.5.3 Temperature Control Loop to Preheat SMR Feed

The diagram below depicts a temperature control loop prior to the entry of the process
fluid into SMR. It is important to control the inlet temperature to SMR because it will affect the
methane conversion in the SMR. The inlet temperature to SMR can be controlled by varying the
flow of the SMR effluent through heat exchanger, HX-102. In this case, the temperature of the
preheated SMR feed is the controlled variable, while the flow of the SMR effluent is the
manipulated variable.

A cascade control loop is employed as follows:


1. The master controller is TIC-101, and the temperature of preheated SMR feed serves as
the set point for the slave controller, which is 539oC.
2. The two control loops are nested, with the secondary control loop (for the slave controller,
FIC-103) located inside the primary control loop (for the master controller, TIC-101)

Production of Hydrogen via Syngas Route 11-7


CN 4120: Design II
Team 32 Instrumentation & Control

Fig 11-4: Control scheme for temperature control loop to preheat SMR feed

The advantage of cascade control is to ensure a swift detection of any flow rate deviation
of the SMR effluent for which necessary adjustments will be made by FIC-103 before an upset in
the temperature of the preheated SMR feed can be effected. This provides a fast response to
deviations from set point values and a feed-forward control loop for the secondary control loop is
subsequently adopted for a faster response time.

11.5.4 Composition Analyzer for SMR Effluent

The composition analyzer A-004 can be used to determine reaction completion by


measuring the methane content of the effluent stream. The composition analyzer can be either an
infra-red or a chromatographic analyzer [R2] which measures a range of 0 to 10% methane in the
background of hydrogen and carbon monoxide. The advantage of using this composition
analyzer in that a desired furnace temperature profile can be arrived at by manipulating the
furnace temperature to achieve the desired degree of conversion.

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CN 4120: Design II
Team 32 Instrumentation & Control

11.6 DETAILED CONTROL DESIGN FOR SMR FURNACE

11.6.1 Air-to-Fuel Ratio Control

Operating without sufficient air can lead to fuel wastage due to inefficient combustion of
air and can even escalate to a hazard when the flammable products of incomplete combustion
ignite in the convection section.[3] However, excess air can reduce the efficiency of the furnace
due to large volumes of air heated to exit stack temperature without producing useful heat
transfer. From the above mentioned points, it can be seen that having an air-to-fuel ratio control
is crucial for the safe and efficient operation of furnace.

Fig 11-5: Control scheme for air-to-fuel ratio control

The air-to-fuel control scheme shown above is designed to fix the excess air at 15% to
ensure complete and stable combustion. In this control scheme, the disturbance variable is the
flow rate of the furnace fuel while the manipulated variable is the combustible air flow. The flow
rate of furnace fuel, which is a combination of PSA purge gas and natural gas, is measured and
transmitted by FT-106 to the ratio station FY-106. At the ratio station, this signal is multiplied by
an adjustable gain whose value is the desired ratio. The output signal from the ratio station will

Production of Hydrogen via Syngas Route 11-9


CN 4120: Design II
Team 32 Instrumentation & Control

act as the set-point for feed-forward controller FIC-107 to control the valve opening of
diaphragm valve FCV-107 to adjust the flow of combustion air to the burners of furnace so as to
maintain the excess air at 15%.

11.6.2 Temperature Control Loop to Regulate Effluent Exit Temperature

Natural gas is burned in the furnace to supply the heat duty required for the endothermic
conversion of methane to hydrogen. Therefore, in this control system, the manipulated variable is
the flow rate of natural gas, while the controlled variable is the temperature of the SMR effluent
being heated.

Fig 11-6: Control scheme for temperature loop to regulate effluent exit temperature

A cascade control loop is employed as follows:


1. The master controller is TIC-105, and the temperature of SMR effluent serves as the set point
for the slave controller
2. The two control loops are nested, with the secondary control loop (for the slave controller,
FIC-105) located inside the primary control loop (for master controller, TIC-105)

Production of Hydrogen via Syngas Route 11-10


CN 4120: Design II
Team 32 Instrumentation & Control

This cascade control will ensure that any deviations in the flow rate of natural gas would
be detected and FIC-105 would make adjustments to the flow rate of natural gas even before it
could cause an upset to the SMR effluent temperature. This is the advantage of cascade controls,
whereby a second measured variable is located close to the potential disturbance and its
associated controller reacts quickly, where it offers very fast response time to deviations from set
point values. To improve the response time further, a feed-forward control loop for the secondary
control loop was employed.

11.6.3 Pressure Control Loop to Regulate Furnace Draft

Fig 11-6: Control scheme for pressure control loop to regulate furnace draft

A pressure control loop is designed to maintain a small negative pressure at the top of the
radiant section just before the convection section. This is because if the pressure is positive in the
radiant section, it will cause the hot flue gas to leak outward and damage the steel structure of
furnaces, thus shortening the lifespan of furnace.

The pressure can be maintained at negative pressure by adjusting the opening of the stack
damper using a feedback control. When the pressure before the convection-section inlet deviates
from the set-point value, the pressure transmitter PT-001 will send a signal to pressure controller
PIC-001 in the feedback control loop which will then adjust the opening of the stack damper to

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CN 4120: Design II
Team 32 Instrumentation & Control

either increase or decrease the draft. In general, when the stack damper closes, the draft
decreases and vice versa. A position transmitter ZT-001 will measure the opening of the stack
damper and reflect it via the indicator ZI-001.

11.6.4 Flue Gas Exit Temperature Control

Flue gas exit temperature control is necessary for two reasons: 1) to prevent corrosion
attack caused by acid gas condensation and 2) to conform to governmental regulation for flue gas
exit temperature. The temperature control at the stack exit is achieved by a cascade control
configuration which consists of a primary control loop utilizing TT-104 and TIC-104 and a
secondary control loop that controls the flow of condensate via FT-104 and FIC-104.

The exit flue gas temperature will be measured by the temperature transmitter TT-104
and will be used by the master controller TIC-104 to establish a set point for the secondary loop
controller, FIC-104.

Fig 11-7: Control scheme for temperature control loop for flue gas exit

Production of Hydrogen via Syngas Route 11-12


CN 4120: Design II
Team 32 Instrumentation & Control

The reason why cascade control is used here instead of conventional feedback control is
because if feedback control is used and there is variation in the flow of the condensate steam
which cause a change in flue gas temperature, this change can only be effected after the
temperature controller takes corrective action to adjust the condensate flow. In our case where
cascade control is used, the flow controller FIC-104 will respond very fast to hold the condensate
flow at its set point without causing any disturbances to the flue gas temperature.

11.6.5 Tube Metal Temperature Indicator

Reformer tubes are designed to operate at a particular pressure and temperature.


Conditions such as flame impingement, poor radiant-heat distribution, interior tube deposits
(coke) can cause localized overheating of tube known as hot-spots, which could result in high
temperature creep. Hence, it is mandatory to have a temperature monitoring device to monitor
furnace tube skin temperature to prevent the plastic deformation of tubes.

Fig 11-8: Tube metal temperature indicators

To achieve this, thermocouples can be welded onto reformer tubes. In addition,


temperature high alarms should also be incorporated together with the thermocouples to alert
operators of high tube skin temperature. This practice is adopted in our design of the steam
methane reformer as a safeguard against tube failure. A common practice in industry requires the

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CN 4120: Design II
Team 32 Instrumentation & Control

installation of thermocouples on 15% of the reformer tubes but due to space constraints on P&ID,
only 4 thermocouples are reflected.

11.6.6 Analyzers for Furnace Control

Analytical devices such as oxygen analyzers and combustible detectors are used to
control the operation of the furnace. The oxygen sensor A-002, which is a solid state heated
zirconium oxide probe that is inserted directly in the stack, can be used to measure the oxygen
content in the flue gas in order to compute the excess air that is being delivered. As such, the
efficiency of furnace combustion can be maximized by throttling the air entering the furnace to
maintain the oxygen content at a desirable value. The sensor can also be tied to a low oxygen
alarm to warn operators if a hazardous furnace atmosphere is developing.

Furthermore, a combustible analyzer A-003, which uses an infra-red beam directed


across the stack to measure the amount of carbon monoxide content in the flue gas, is also
utilized for furnace control. The combustible analyzer usually works in tandem with an oxygen
analyzer to provide a correlation between excess air and unburned fuel going up the flue stream.

For this reason, they can serve as a form of backup to check for the effectiveness of the
air-to-fuel ratio control loop. Although combustible analyzers can sometimes be used to
automatically adjust the air/fuel ratio, this control scheme was not adopted in our control of
furnace due to reliability issue of the combustible analyzer.

11.7 Safety Devices

11.7.1 Pressure Relief Valves

Relief valves are required to provide an outlet for over-pressurised fluids to prevent
rupture of pipelines so as to protect operators from possible hazards of over-pressurizing
equipment. In addition, relief valves also prevent damage to adjoining property; reduce insurance
premiums and chemical losses during pressure upset. With these in mind, it is in fact stipulated
by governmental regulations that installations of pressure relief systems are compulsory.

Production of Hydrogen via Syngas Route 11-14


CN 4120: Design II
Team 32 Instrumentation & Control

In this preliminary piping and instrumentation diagram (P&ID) design of the SMR
reactor/furnace, the pressure relief devices are designed to be installed at every point identified
as potentially hazardous. Since most of the pipelines are in gas service, safety valves are chosen
for pressure relief. Safety valves pop open to release the excess pressure when the operating
pressure exceeds the set pressure. The only exception is the pipeline with steam in service.
Hence a safety relief valve, which functions as relief valve for liquid and safety valve for steam,
may be required [R4].

11.7.2 Process Alarms

The function of a process alarm is to warn operators of impending dangers when process
parameters such as temperature, pressure, flow or level exceed or fall below the permissible
limits. In general, alarms can be categorised as follows [R5]:

Type Description Function


Equipment status Indication to whether an equipment is switched
Type 1 Alarm
alarm on or off
When activated, it acts as an indication that the
Abnormal
Type 2 Alarm reading taken by the sensor is outside
measurement alarm
acceptable limit
Alarm that is directly triggered by process
An alarm without instead of sensor signal when the process
Type 3 Alarm
an adjoining sensor parameter is out of specification. Knowledge of
actual process value is not required
An alarm with an Serve as a backup to the regular sensor in the
Type 4 Alarm
adjoining sensor event that it fails
Automatic
Type 5 Alarm shutdown or start- Typical type of alarm that is widely used
up system
Table 11-2: Summary of different categories of alarm

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CN 4120: Design II
Team 32 Instrumentation & Control

Upon activation of the alarm, an annunciator, either in the form of visual displays
(flashing light on control panels) or audible sounds (horns or bells), will be triggered. Unless
acknowledged by plant operators, the alarm will remain in activation. If the abnormal situation
that sets off the alarm is deemed to be potentially dangerous, an automated corrective action will
be initiated by the safety interlock system to shut down the affected unit.

Excessive number of unnecessary alarms should be avoided because frequent “nuisance


alarms” make plant operators less responsive to crucial alarms and may obscure the root cause of
the abnormal situation in the presence of many unimportant alarms. Hence, alarms should only
be installed at locations deemed absolutely necessary. The alarms in the P&ID and their
functions are summarized in the following table:

Alarm Tag No. Description for Alarm Cause


THA -104 Flue Gas High Temperature
THA-201, THA-202, THA-203, THA-204 SMR Furnace High Tube Skin Temperature
ALA-002 Low Flue Gas Oxygen Content
PHA -001 SMR Furnace High Pressure
FLA -201 Fuel Gas Low Flow
FLA -202 Combustion Air Low Flow
FLA -203 SMR Feed Low Flow
FLA -204 SMR Effluent Low Flow
Table 11-3: Summary of alarms in our P&ID and their causes

11.7.3 Safety Interlocks or Emergency Shutdown System (SIS or ESD)

The control loops that are designed in the P&ID form the basic process control system
(BPCS) which acts as primary protection against deviations in process parameters. During
normal operations, BPCS can provide acceptable control but this may not be the case during
abnormal or emergency situations. For this reason, implementation of SIS or ESD is required to
serve as a backup especially when BPSC components malfunction or when there is utility failure.
As such, considerations must be made for SIS and ESD to function independently of the BCPS.

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Team 32 Instrumentation & Control

In view of the drastic measure such as the complete shutdown of process unit, the SIS
and ESD can only be considered as the last resort to protect the equipment and prevent injury to
personnel and used only when critical process variables go beyond the specified allowable
operating limit. Although SIS is essential for safe plant operation, unnecessary plant shutdown
should be precluded as it can reduce throughput due to downtime and may cause products to go
off-specification during subsequent plant start-up.

11.7.3.1 Implementation of SIS or ESD for the protection of nickel catalyst

Fig 11-9: SIS control scheme for protection of nickel catalyst

As mentioned earlier, a low steam/methane ratio is undesirable because it can deactivate


the nickel catalyst due to coke formation. To prevent this situation from arising, a SIS should be
in place to tackle any abnormalities in the ratio. The SIS to be implemented is illustrated in the
above control scheme. When the steam/methane ratio falls below the limit of approximately 3:1,
a flow switch FSL-001 will trigger off an alarm. If the ratio continues to fall below the critical
limit (approximately 2.7:1), the natural gas stream will be shut off via FSL-002, which trips a
solenoid that control the transducer I/P-101 and causes FCV-101 to be closed.

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Team 32 Instrumentation & Control

In designing such a SIS, several points must be taken into consideration. Firstly, FCV-
101 must be a quick-closing valve (4 to 5 seconds for full closure) so that the flow of natural gas
can be almost instantly stopped when there is a large deviation in reforming steam, thus
protecting the reformer catalyst. FCV must also be a single-seated tight shut-off valve, to prevent
leakage during the time while the electric-operated shutoff valve is in the process of closing.

11.8 Additional Considerations in Process Control

11.8.1 Redundancy of Air Blowers and Expanders

The reliability of plant equipment is critical to successful plant operation. Hence, spare
air blowers and expanders are provided in parallel to the commissioned equipment and are
placed on hot standby to ensure the continuous operation of the hydrogen plant whenever any of
the equipment undergo mechanical failure or are sent offline for maintenance purposes, which is
a common phenomenon during normal operation.

Fig 11-10: Redundancies used in process control

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Team 32 Instrumentation & Control

11.8.2 Isolation Valves and Bypass

Isolation valves, most commonly gate valves, are installed upstream and downstream of
process equipment such as heat exchangers, air pre-heater, control valves and air blower to
ensure the operability of the plant whenever there is maintenance or repair of the equipment.
When isolated, a bypass as illustrated must be present to divert the process flow to the other side
of the process equipment.

B/P

Fig 11-11: Bypass of pipelines

11.9 REFERENCES

[R1]: Seborg D. S., Edgar T. F., Mellichamp D. A. Process Dynamics and Control, John Wiley
& Sons (2004)
[R2]: Liptak B. Instrument Engineer’s Handbook: Process Control and Optimization, CRC Press
(2005)
[R3]: Lieberman N. P., Lieberman E. T., Working Guide to Process Equipment. 2nd Edition Mc-
Graw-Hill
[R4]: Crowl D.A., Louvar J.F. Chemical Process Safety: Fundamentals with Applications. 2nd
Edition, Prentice Hall PTR (2002)
[R5]: Connell, B., “Process Instrumentation Applications Manual”, Mc-Graw-Hill, New
York (1996)

Production of Hydrogen via Syngas Route 11-19


E-105

A CONDENSATE
ZI ZT
001 opacity PSV-008
MAKEUP NATURAL GAS 001 001

INTAKE FILTER
TO FURNACE
AIR FROM

THA
E-106
104
ALA
002 TT TIC PSV-009
O2 TE
104 104 104
I/P FIC
A
B-101 001 A
002 O2 AP-101 104
003 CO AP-102 I/P
104
PSV-007
COMBUSTION AIR

PSV-010
FT
104
PSV-006

PSA PURGE GAS


( CO removed)
TE
NATURAL GAS 103
B-102 FROM PIPELINE

2
TI FT
103 107 FT
105

TI TE
FLA
102 102
203
PI
I/P
FI FIC 101 PHA PIC 107 FIC I/P
203 103 001 001 105 105

FT 42 BAR HP STEAM
PSV-005 FIC
203 FOR EXPORT
I/P PT FLA 107
101 I/P 001 202
TT TIC 103
FT TE
101 101 103 203
FT FI
THA TI 202 202
FIC SMR EFFLUENT FY
203 203
101 106
HX-102

FT
101 TI TE F-101
201 201 FLA FI FT
201 201 106

THA TE
HX-101 202
201 PSV-012
See Detail A

TI
FY E-101
202 TE
101 204
PSV-002
THA
202 TI
204
E-102
FIC THA
102 204
PSV-001 SMR EFFLUENT TO
HX-102
PSV-011
TE TT TIC
I/P AT PI FT
105 105 105
102 004 102 204
FT
E-103 Detail A
102
FI FLA
A PIC
IMPORTED PSV-003 204 204
STEAM 004 Methane
PT

E-104

PSV-004
Applicable to all expanders

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