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TEAM 32:
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.
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,
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.
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
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.
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.
SMR
HTS
Furnace
LTS & K/O Drum
PSA
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
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
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
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:
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.
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.
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.
With such encouraging advantages, the steam reforming process remains as the
most mature and established form of technology to produce hydrogen [R3].
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:
The following table adapted from literature shows the some of the noteworthy
features for the various choices of reforming feedstock:
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
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.
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.
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.
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%).
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.
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.
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.
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.
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.
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
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:
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.
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.
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).
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.
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
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.
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].
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.
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.
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.
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.
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.
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
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.
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.
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
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.
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
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.
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.
Fig 2.4.4.1a:
Conversion
Profiles from
MATLAB
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.
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
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.
Selection of reactor materials has been made via the following considerations [R15].
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.
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:
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.
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).
Fig 2.5.3a: Estimation of furnace tube life for a given set of operating temperature & pressure
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.
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.
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.
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.
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.
2.8 NOTATIONS
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.
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.
2.12 APPENDIX
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');
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');
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
%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.
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
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
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)
η 2 r2 + η 3 r3
η CO = Eqn (2-29)
2
r2 + r3
− (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)
− ( −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
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)
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.
Figure is retrieved from Midrex from World Wide Web on 19th March 2008 at:
http://www.midrex.com/uploads/documents/Catalyst(1)1.pdf.
Chapter 3 : FURNACE
3.1 INTRODUCTION
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.
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.
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
To calculate the heat released from combustion and the temperature of the products
formed, the enthalpy change of the combustion process can be considered2.
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.
∆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
The flame T is quite close to the original flame temperature calculated and hence flame T will
be taken to be 1390°C.
Given the furnace profile: Furnace Effficiency = (Heat to process) / (Heat released by fuel)
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
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
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.
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.
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.
Turndown consideration
However, as the furnace supports a reaction process, recycling will not be considered.
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.
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)
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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
3.2.8.9 Two main equations that will be used for iteration to find Tg (flue gas temp)
Tg + 460 4 T + 460 4
+ 7(Tg − Tt )
QR
= 1730 − t
αAR F 1000 1000
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.
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
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)
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)
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.
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.
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
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.
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
Dimensions and tube material as provided by Heat Exchanger Network (HEN) counterpart:
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.
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
The pressure drop for the following streams is computed. For the SMR stream,
pressure drop through bends is neglected as the tubes are straight.
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.
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.
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
The stack exit loss is computed as follows: ∆P1 = 0.176 KV g2 / (Ta + 273)
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
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
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
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.
Pd = 0.35 H g Patm 1 − 1
aT T ga
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.
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.
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
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.
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.
Preliminary cost estimation was done to estimate the furnace and its auxiliary
equipment cost using the CAPCOST program developed by Turton.
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)
(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
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.
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)
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.
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.
Natural gas feed is not considered for furnace operation as the off gas from the PSA is
sufficient to supply enough heat energy required.
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.
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.
3.9 REFERENCES
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.
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.
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]
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:
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.
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).
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:
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:
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
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
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
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
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.
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)
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
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.
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.
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)
4.6 REACTOR
An adiabatic single fixed bed catalytic reactor is used for the HTS 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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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
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
Calculations
The pressure drop against aspect ratio figure is plotted as shown below:
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)
The MATLAB program used to solve this can be found in Appendix 4.12.3.
Catalyst cost
Vessel Costs
From the literature data [1], the vessel cost can be estimated as follows:
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.
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.
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.
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.
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.
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
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.
∆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
Q 4.4622 × 10^ 6
AΟ = = = 915.3m 2
U × ∆Tm 540.1 × 9.02
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.
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
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
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.
5
∆Pt = 2 × (8 × 0.045 × + 2.5) × (0.5 × 7.661 × 27.7512 ) = 722739 Pa = 722kPa
0.015
4.9 CONCLUSION
These give a good idea on the design of the HTS reactor as well as the cost of building the
reactor.
4.10 NOTATIONS
∏ i
: product over all species i
ψ : activity factor
k : rate constant
K : equilibrium constant
yi : mole fraction of species i
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
4.12 APPENDICES
Appendix 4.12.1
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);
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>0.03,
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;
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
Wt=i*200/2.2;
plot (x,y);
plot (x,a);
Appendix 4.12.2
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;
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
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);
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:
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]
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.
Rase (1977) has come up with the following equation for application to the shift conversion:
(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).
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)
Fig.4
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.
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/
(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.
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.
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.
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
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)
(5-8)
and
(5-9)
(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
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)
(5-15)
At ω = 1
(5-16)
(5-17)
(5-18)
(5-19)
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
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.
(5-20)
where nA is the molar flow rate of component A, and the rate of reaction is given by (Rase,
1977)
(5-21)
(5-22)
(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)
(5-25)
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)
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)
(5-31)
where
(5-32)
(5-33)
and
(5-34)
(5-35)
and
(5-36)
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
(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.
(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)
The external mass transfer in the pellet equation takes the form
(5-45)
(5-46)
where RG= the universal gas constant and T = average temperature for the catalyst bed.
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.
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.
For the HTS unit, inlet’s molar flow of H2O and CO is as follows:
For the LTS unit, inlet’s molar flow of H2O and CO is as follows:
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.
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:
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 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.
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
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)
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.
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:
(4-53)
(4-54)
(4-55)
(4-56)
(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.
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.
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
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
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.
• 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
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.
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.
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.
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
(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)
(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
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
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
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.
LITERATURE REVIEW
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.
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
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.
CONCLUSION
Diameter Height
Dimensions 3.31 4.07
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.
BIBLIOGRAPHY
APPENDIX A1
Matlab codes
• Calculation of Catalyst Weight and Outlet Compositions
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);
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);
rateavg= (rate+rate1)/2;
Fco = Fco1;
Fh2o = Fh2o1;
Fco2 = Fco21;
Fh2= Fh21;
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;
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);
6.1 INTRODUCTION
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.
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:
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%.
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.
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
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.
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.
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.
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.
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).
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.
∂ 2 cA ∂c ∂v ∂c 1− ε ∂qA
− DL 2 + v A + cA + A + =0
∂z ∂z ∂z ∂t ε ∂t
∂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
∂qB e ∂qA
= kB (qB − qB ) e
= kA (qA − qA )
∂t ∂t
∂P
= 0 (For Adsorption and Purging steps)
∂τ
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
The 5 dimensionless equations were inputted into COMSOL for simulation with the set of
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 )
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]:
• Adsorption and Desorption time should be kept constant for 2 bed processes.
• 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.
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
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.
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.
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.
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.
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
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 )
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)
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.
1.00000
0.99950
0.99900
Purity
0.99850
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
Recovery = 82.0%
Purity = 99.9%
where total time is time taken for both pressurization and high pressure adsorption to occur
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.
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
C po = 850 × 60 = $ 51,000
( P + 1) D
+ 0.00315
2[850 − 0.6( P + 1)]
Pressure factor, FP ,vessel = for t vessel > 0.0063m pp925 [1]
0.0063
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 = 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,
= 60 × (1-0.36) × 850
= 32,640 kg
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.
= $ 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
= $ 1,490,066
= $ 1,490,066 × 1.1
= $ 1,639,073
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%).
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.
6.10 NOTATIONS
Vf Minimum g Gravitational
fluidization velocity acceleration (m/s2)
Subscripts
A CO2 s Saturated
B H2 H, L High, low
6.11 APPENDIX
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
εA
= 190
κ σ A = 3.996
εB σ B = 2.968
= 33.3
κ
Ω D = 0.88216(int erpolate)
∂ 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
∂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
∂ 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
c A + c B = C ≠ f (z ) and
∂ 2 C ∂C
= =0
∂z 2 ∂z
∂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
∂ 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
∂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
∂ 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
Temperature 323K
High P 2.5e6 Pa
Low P 1e5 Pa
6.13 REFERENCES
[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)
[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
[11] Turton et al, Analysis, Synthesis, and Design of Chemical Processes, 2nd edition,
Prentice Hall, 2007
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.
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.
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.
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.
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
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
the exchanger to allow for a performance reduction in actual operations. The list of fouling
factors used is included in the following
Table 3.
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.
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:
Rate of return(% )
1 +
AF =
100
Plant life
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.
=
(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
=
(Cost of cooling water )(Plant operation time )
(Mass density )(mass heat capacity )(Temperature difference )
=
(US $0.067 m )(28800000 s yr )
3
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.
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%).
be applied.
Figure 4: (Right) Utility composite curve showing the utility pinch created by HP steam generation.
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.
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.
4. Hot utilities are added up to meet the heating energy targets, and no cold utilities are used
above pinch.
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.
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.
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.
7.3.4.1 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
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.
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.
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.
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.
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.
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.
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.
7.5.5 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
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.
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.
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:
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
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.
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
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.
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.
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.
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
This was taken to be the final heat exchanger specification as shown in Table 7.
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
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
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.
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.
Figure 14: Integrated heat exchanger network with PFD of proposed hydrogen plant.
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
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
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
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
_
2
L = loading factor ( lb H 2O / ft Base Area )
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]
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.
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.
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
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]
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.
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%
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
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)
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
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
−
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)
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.
_
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.
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.
kg
= 5746 2
hr.mbase area
Assumption made: Density of cooling water does not change with temperature (1000 kg/m3)
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
The required base area or cross-sectional area (B) can be determined from the below equation:
L 1.488 × 106
B= −
= = 260m2
L 5746
In the cooling tower system, water makeup is required to replace the cooling water which is
lost through evaporation, drift and blow-down.
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
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
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
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.
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
Hence,
1.488 ×106 × 2.20462262 × 29.86
Pp =
1.98 × 106 × 0.80
= 61.84 hp
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 )
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
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.
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.
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]
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.
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
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.
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.
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.
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.
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.
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
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
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.
Hence,
Cost of makeup water = 0.067 × 66.96 × 8000 = US $35,890.56 / yr
The total power requirement is the summation of pump power and fan power
PTotal = PF + Pp = 62 + 81 = 143hp
Optimization of the cooling tower is performed to minimize the operating and construction
cost of the cooling tower. The variable that is changed is the exit air temperature. From the
calculations shown above, it is clear that when exit temperature air temperature differ, the
−
L KaV
ratio, the tower characteristic − , the tower dimensions and the power consumption by
G L Cp
fan and pump will vary. The parameter that will not change during varying exit air
temperature is the makeup water requirement. Hence, it is not used as a guideline for
optimization.
60000
700000
50000 600000
C o n s tr u c ti o n C o s t
500000
Operating Cost (US$)
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
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.
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].
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.
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.
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.
8.9 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
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
Power Requirement
Pump Head 9.10 m
Fan Power 80 hp
Material of Construction
Cooling Tower Stainless Steel
Fill PVC
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.
8. Seider W.D., Seader J.D., Lewin D.R. Product & Process Design Principles. Edition 2
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
9.1 INTRODUCTION
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
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.
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.
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.
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.
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)
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
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
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
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
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
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
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.
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
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
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
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
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
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
The raw materials used in this plant are natural gas and high pressure steam.
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
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
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
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.
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.
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)
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.
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.
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.
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
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.
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.
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.
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:
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.
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.
Fig 9-4: Plot plan of storage tanks for natural gas feed
Initial capital cost will constitute the 3 tanks as well as piping, heater and cooler.
Based on CAPCOST,
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$1,551,600
Land Area needed (m3) Unit cost for land (US$/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
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:
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
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.
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.
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
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.
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.
REFERENCES
[R1]: Turton R., Bailie R.C., Whiting W.B. and Shaeiwitz J.A., “Analysis, Synthesis, and Design
of Chemical Process”, Prentice Hall, 2003
[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
10.1 INTRODUCTION
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.
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.
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
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
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
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
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
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
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
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
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
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
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
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
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
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:
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.
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].
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
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
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].
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.
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.
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.
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.
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].
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].
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].
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.
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.
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].
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
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].
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.
From Figure 10-1, the plant area was estimated to be around 29400 m2.
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.
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.
10.4.3 Ventilation
Ventilation [R1] is extremely important for this plant for the following reasons:
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.
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
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
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.
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
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.
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
the global
warming
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
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,
nausea,
vomiting,
loss of
consciousnes
s and death
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
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
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.
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.
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.
As can be seen from our mitigation measures, we are actively fulfilling the above mentioned
objectives of the NEEC.
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
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.
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.
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.
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
[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
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.
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.
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:
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
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
Table 11-1: Summary of advantages and disadvantages of feedback and feed-forward control
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].
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
5. Choose output variables that have favourable dynamic and static characteristics
3. The manipulated variables should affect the controlled variables directly rather than
indirectly
3. Select measurement points that minimize time delays and time constraints
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.
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.
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.
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.
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.
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.
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.
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
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%.
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
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.
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
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.
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
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.
installation of thermocouples on 15% of the reformer tubes but due to space constraints on P&ID,
only 4 thermocouples are reflected.
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.
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.
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.
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].
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]:
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.
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.
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.
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.
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.
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
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)
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
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