RETROFITTING ANALYSIS TO INTEGRATE THE MIXALCO PROCESS TO THE CRUDE OIL DISTILLATION PROCESS

Thesis By LAURA PATRICIA PRADA VILLAMIZAR

Submitted to the Office of Graduate Studies of Universidad de Los Andes In partial fulfillment of the requirements for the degree of

M.SC. CHEMICAL ENGINEERING

August 2013

Major Subject: Chemical Engineering

Retrofitting analysis to integrate the MixAlco process to the crude oil distillation process Copyright 2013 Laura Patricia Prada Villamizar

RETROFITTING ANALYSIS TO INTEGRATE THE MIXALCO PROCESS TO THE CRUDE OIL DISTILLATION PROCESS

Thesis By LAURA PATRICIA PRADA VILLAMIZAR

Submitted to the Office of Graduate Studies of Universidad de Los Andes In partial fulfillment of the requirements for the degree of

M.SC. CHEMICAL ENGINEERING

Approved by: Chair of committee, Committee Members, Head of Department, Roco Sierra Ramrez, PhD. Jorge Mario Gmez, Phd. Oscar Alvarez Solano, PhD.

August 2013

Major Subject: Chemical Engineering

ABSTRACT Retrofitting analysis to integrate the MixAlco process to the crude oil distillation process (August 2013) Laura Patricia Prada Villamizar, Universidad de los Andes, Colombia Advisor: Roco Sierra Ramrez, Ph.D. The MixAlco technology comprises a processing facility to produce liquid transportation fuels and/or value-added chemicals from biomass resources; however, build and run a new MixAlco plant may be very costly. On the other hand, high quality and easily exploitable fossil-fuels resources inevitably dwindle worldwide. Both the preservation of high quality fossil-fuel resources and the feasibility of a MixAlco plant can be importantly enhanced by retrofitting the MixAlco process into an existing fossil-fuel processing facility. This retrofitting is attainable because both processes have similar products (bio-gasoline, gasoline, bio-jet, jet). This work assesses a retrofitting analysis to integrate the MixAlco process to a selected case of crude oil distillation process (CODP). The proposed methodology suggests a hierarchy cost using the following tools: process simulations, mass and energy integrations, and economic evaluations. The work starts by assessing improvements for a base case of each of the two involved plants separately. Then, comparisons between base cases and the retrofitting of both processes (the resulting plant is regarded here as integrated bio refinery) is made. The most remarkable result was a Net Present Value (NPV)

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increment from MM USD 7.30 to MM USD15.7, and Return On Investment (ROI) increment from 11.1% to 12.4% for MixAlco process.

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RESUMEN Retrofitting analysis to integrate the MixAlco process to the crude oil distillation process (August 2013) Laura Patricia Prada Villamizar, Universidad de los Andes, Colombia Advisor: Roco Sierra Ramrez, Ph.D. MixAlco es una tecnologa donde se producen combustibles lquidos de transporte y / o productos qumicos de valor agregado a partir de fuentes de biomasa, sin embargo, construir y operar una planta nueva de MixAlco puede ser muy costoso. Por otro lado, los recursos combustibles fsiles de alta calidad y fcilmente explotables disminuyen en todo el mundo. La preservacin de los combustibles fsiles de alta calidad y la viabilidad de una planta MixAlco, pueden mejorarse mediante la integracin del proceso MixAlco en una instalacin existente de procesamiento de combustibles fsiles. Esta integracin es posible gracias a que ambos procesos tienen productos similares (bio-gasolina, gasolina, bio-jet, jet). Este trabajo evala un anlisis de integracin entre el proceso de MixAlco con el proceso de destilacin de crudo de petrleo (PDCP) como caso seleccionado. La metodologa propuesta sugiere una jerarqua de costos con las siguientes herramientas: simulacin de procesos, integraciones de masa y energa, y evaluaciones econmicas. Este trabajo inicia evaluando mejoras para un caso base en cada una de las plantas involucradas por

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separado. Despus, se hacen comparaciones entre los casos base y la integracin de los dos procesos (la planta resultante se considera como "bio-refinera integrada"). El resultado ms importante para el proceso de MixAlco presenta un incremento en el Valor Presente Neto (VPN) de MM USD 7.30 a MM USD 15.7 y un incremento en la tasa interna de retorno de la inversin (TIR) de 11.1% a 12.4%

ACKNOWLEDGEMENTS

I would like to thank my family for the love, belief, and support they have provided me throughout my life, especially to my mother, Laura Villamizar. She gave me much love and support, and thanks to my two brothers Dany and Sergio. I would like to thank my two big loves Guillermo and Santiago, for their compression, support and company all the time, especially during this work. I would to express my deepest gratitude to Dr. Roco Sierra, for her guidance, and for her patience throughout this work. Thank you for all support during my graduate study. I would like also to thank to all her group members for all their support and help. I would like also to thank Cesar Mahecha for the support that he provide me during this work.

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NOMENCLATURE AEA: Aspen Energy Analyzer AFC: Annualized Fixed Cost AGO: Atmospheric Gas Oil APEA: Aspen Process Economic Analyzer API: Standard API gravity BPD: Barrel Per Day C: Cooler CE: Chemical Engineering Plant Cost Index CM: Compressor CODP: Crude Oil Distillation Process CON: Conveyor CSTR: Continually Stirred Tank Reactors DHFORM: Formation Enthalpy DW&B: Direct Wage and Benefits E: Heat Exchanger EIA: US Energy Information Administration FCI: Fixed Capital Investment FOB: Free On Board FOC: Fixed Operating Cost

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GAL: U.S liquid gallon, (231 in3) GCC: Grand Composite Curve H: Heater HEN: Heat Exchange Network HVGO: Heavy Vacuum Gas Oil IRR: Internal Rate of Return INHSPCD: In-house Pure Component Database LVGO: Light Vacuum Gas Oil M: Mixer MACRS: Modified Accelerated Cost Recovery System MOC: Minimum Operating Cost MM: Million MR: Cumulative Mass Lost MS: Marshall and Swift Cost Index MSA: Mass-Separating Agent MTAC: Minimizing Total Annualized Cost MW: Molecular weight MW&B: Maintenance Wages and Benefits Net_G: Net Generation NF: Nelson-Farrer Refinery Construction Index

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NPV: Net Present Value NREL: National Renewable Energy Laboratory NRTL: Non-random-two-liquid P: Pump PBP: Payback Period PSA: Pressure Swing Adsorption R: Reactor ROI: Return On Investment RKS: Redlich-Kwong-Soave S: Splitter SCF: Standard Cubic Foot SG: Standard specific gravity at 60F SP: Separator T: Distillation tower TBP: True Normal boiling point TCI: Total Capital Investment TEHL: Table of Exchangeable Heat Loads TID: Temperature-Interval Diagram TK: Tank TR: Turbine

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TON: Metric ton (1,000kg) USD: United States dollars VFAs: Volatile Fatty Acids VLSTD: Standard Liquid MolarVolume at 60F VOC: Variable Operating Cost VP: Venture Profit VS: Volatile Solids WCI: Working Capital Investment WWT: Waste Water Treatment ZC: Critical Compressibility Factor

TABLE OF CONTENTS Page ABSTRACT .............................................................................................................. RESUMEN ................................................................................................................ ACKNOWLEDGEMENTS ...................................................................................... NOMENCLATURE .................................................................................................. TABLE OF CONTENTS .......................................................................................... LIST OF FIGURES ................................................................................................... LIST OF TABLES .................................................................................................... 1. INTRODUCTION ............................................................................................... 2. OBJECTIVES ..................................................................................................... 2.1 General objective..................................................................................... 2.2 Specific objectives................................................................................... 3. METHODOLOGY .............................................................................................. 3.1 Description of the proposed methodology .............................................. 3.1.1 Define needs ................................................................................. 3.1.2 Process arrangements .................................................................. 3.1.3 Feasibility .................................................................................... 3.2 Simulation Tools ........................................................................................... 3.2.1 MixAlco process base case ........................................................ 3.2.2 CODP base case ............................................................................ 3.2.3 MixAlco process and CODP retrofitted plant ............................ i iii v vi x xiii xv 1 5 5 5 6 6 6 7 7 9 9 11 14

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Page 3.3 Process integration ........................................................................................ 3.3.1 Material rerouting .......................................................................... 3.3.2 Heat Exchanger Network (HEN) .................................................. 3.3.3 Cost Analysis................................................................................. 4. RESULTS AND DISCUSSION ................................................................... 4.1 Simulation results .................................................................................... 4.1.1 Simulation builds up and results for MixAlco base case ......... 4.1.1.1 MixAlco block description .......................................... 4.1.1.2 MixAlco overall mass balance results......................... 4.1.1.3 MixAlco overall heat balance results .......................... 4.1.2 Simulation builds up and results for CODP base case ................ 4.1.2.1 CODP Block description ................................................ 4.1.2.2 CODP overall mass balance results ............................... 4.1.2.3 CODP overall heat balance results ................................. 4.2 Define needs ............................................................................................ 4.3 Retrofitting procedure applied: Process arrangements............................ 4.3.1 Internal rearrangements ............................................................... 4.3.1.1 MixAlco process ......................................................... 4.3.1.2 CODP ............................................................................. 4.3.2 Internal modifications ................................................................. 4.3.2.1 MixAlco process ......................................................... 14 15 16 16 19 19 19 21 54 56 57 58 68 69 69 70 70 70 79 84 84

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Page 4.3.2.2 CODP ............................................................................................ 95

4.3.3 External modifications ................................................................ 103 4.3.3.1 Case 1 ............................................................................. 105 4.3.3.2 Case 2 ............................................................................. 110 4.3.3.3 Comparison between cases............................................. 123 4.4 Sensitivity analysis .................................................................................. 125 4.4.1 Variation of gasoline prices......................................................... 125 4.4.2 Variation of Jet prices ................................................................. 126 4.4.3 Variation of Biomass prices ........................................................ 127 4.4.4 Variation of MixAlco plant capacity........................................ 127 CONCLUSIONS ....................................................................................................... 129 RECOMMENDATIONS AND FUTURE WORK ................................................... 132 REFERENCES .......................................................................................................... 134 APPENDIX A ........................................................................................................... 137 APPENDIX B ........................................................................................................... 153 APPENDIX C ........................................................................................................... 157 APPENDIX D ........................................................................................................... 159 APPENDIX E ............................................................................................................ 166 VITA ................................................................................................................ 177

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LIST OF FIGURES FIGURE 1-1 3-1 3-2 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 Pathways for converting biomass to hydrocarbon fuels.......................... Flowchart of the proposed methodology ................................................. Crude oil distillation TPB ....................................................................... Blocks of MixAlco process simulation. ............................................... Feed handling simulation ........................................................................ Pretreatment simulation............................................................................ Fermentation simulation .......................................................................... Dewatering simulation ............................................................................ Ketonization simulation .......................................................................... Lime kiln simulation ............................................................................... Final simulation ....................................................................................... Distillation curve for gasoline ................................................................. Page 2 8 13 20 23 25 29 34 39 43 46 49 50 51 57 58 61 63 66 73

4-10 Distillation curve for Jet ............................................................................. 4-11 Gasification simulation... ........................................................................... 4-12 Blocks of CODP simulation ....................................................................... 4-13 First pre-heating train ................................................................................. 4-14 Second pre-heating train............................................................................. 4-15 Atmospheric distillation column ............................................................... 4-16 Vacuum distillation column ....................................................................... 4-17 Mass integration for MixAlco process ....................................................

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FIGURE 4-18 Power integration for MixAlco process .................................................. 4-19 Heat integration in Reactors for MixAlco process .................................. 4-20 Cash flow for MixAlco process in the base case .................................... 4-21 Hot and Cold composite for MixAlco HEN............................................ 4-22 Grand composite curve for MixAlco HEN ............................................. 4-23 Grid diagram for MixAlco HEN ............................................................. 4-24 Cash flow for MixAlco process with HEN ............................................. 4-25 Hot and Cold composite for CODP HEN .................................................. 4-26 Grand composite curve for CODP HEN .................................................... 4-27 Grid diagram for CODP HEN ....................................................................

Page 73 74 79 87 87 89 95 97 97 99

4-28 MixAlco and CODP simulation integrated ............................................. 104 4-29 Cash flow of MixAlco process in case 1 ................................................. 109 4-30 Hot and Cold composite for case 2 ............................................................ 112 4-31 Grand composite curve for case 2 .............................................................. 113 4-32 Grid diagram for case 2 .............................................................................. 115 4-33 Cash flow of MixAlco process in case 2 ................................................. 123 4-34 Variation of gasoline price for MixAlco process .................................... 125 4-35 Variation of Jet price for MixAlco process ............................................. 126 4-36 Variation of Biomass price ......................................................................... 127 4-37 Variation of MixAlco plant capacity....................................................... 128

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LIST OF TABLES

TABLE 3-1 3-2 3-3 3-4 3-5 3-6 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 4-11 4-12 4-13 Biomass feed composition for MixAlco process .................................... MixAlco operating conditions................................................................. Assay data for crude oil .............................................................................. Assay data for crude oil Light ends ............................................................ CODP operating conditions ....................................................................... Feedstock, utilities and product prices ....................................................... Feed handling mass and heat balance ........................................................ Heat balances for Feed Handling equipment ............................................. Pretreatment mass and heat balance ........................................................... Fermentation mass and heat balance .......................................................... Heat balances for Pretreatment and Fermentation equipments .................. Dewatering mass and heat balance............................................................. Heat balances for Dewatering equipments ................................................. Ketonization mass and heat balance........................................................... Heat balances for Ketonization equipments ............................................... Heat balances for Lime kiln equipments .................................................... Lime kiln mass and heat balance................................................................ Final mass and heat balance ....................................................................... Heat balances for Final equipments ...........................................................

Page 10 11 12 12 13 17 24 24 27 30 33 35 38 40 42 43 44 46 49

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TABLE 4-14 4-15 4-16 4-17 4-18 4-19 4-20 4-21 4-22 4-23 4-24 4-25 4-26 4-27 4-28 4-29 4-30 4-31 4-32 4-33 4-34 Gasification mass and heat balance ............................................................ Heat balances for Gasification equipments ................................................ MixAlco yields ........................................................................................ Summary fo heat balances for MixAlco processs ................................... First train preheating mass and heat balance .............................................. Heat balances for equipments in 1st preheating train ................................ Second train preheating mass and heat balance ......................................... Heat balances for equipments in 2nd preheating train ............................... Atmospheric distillation mass and heat balance ........................................ Heat balances for equipments in atmospheric distillation unit .................. Vacuum distillation mass and heat balance................................................ Heat balances for equipments in vacuum distillation unit ......................... CODP Yields .............................................................................................. Overall heat balances for CODP ................................................................ Fresh MixAlco streams ........................................................................... Waste MixAlco streams .......................................................................... VOC of MixAlco process in base case.................................................... FOC of MixAlco process in base case .................................................... FIC of MixAlco process in base case ...................................................... Summary MixAlco economic results in base case .................................. Fresh CODP streams ..................................................................................

Page 52 53 54 56 59 60 62 62 64 65 67 68 68 69 71 72 75 76 77 77 80

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TABLE 4-35 4-36 4-37 4-38 4-39 4-40 4-41 4-42 4-43 4-44 4-45 4-46 4-47 4-48 4-49 4-50 4-51 4-52 4-53 4-54 4-55 Waste CODP Streams ................................................................................ FCI for CODP in base case ........................................................................ VOC for CODP in base case ...................................................................... FOC for CODP in base case ....................................................................... MixAlco process streams for HEN ......................................................... Heat integration for MixAlco process ..................................................... Heat exchangers for MixAlco HEN ........................................................ Coolers for MixAlco HEN ...................................................................... Heaters for MixAlco HEN ...................................................................... VOC of MixAlco process with HEN ...................................................... FOC of MixAlco process with HEN ....................................................... Summary MixAlco economic results with HEN..................................... Process streams for CODP ......................................................................... Summary of HEN cases for CODP ............................................................

Page 81 82 82 83 85 88 90 90 91 92 93 94 96 98

Heat exchangers in the best CODP case .................................................... 100 Coolers in the best CODP case .................................................................. 101 Heaters in the best CODP case ................................................................... 102 VOC of CODP with HEN .......................................................................... 102 Heat integration for MixAlco and CODP in case 1 ................................ 106 VOC of MixAlco process in case 1 ......................................................... 106 FOC of MixAlco process in case 1 ......................................................... 107

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TABLE 4-56 4-57 4-58 4-59 4-60 4-61 4-62 4-63 4-64 4-65 4-66 4-67

Page

Summary MixAlco economic results in case 1 ....................................... 108 Process streams for case 2 .......................................................................... 110 Heat integration for MixAlco and CODP case 2..................................... 114 Heat exchangers for case 2 ......................................................................... 115 Coolers for case 2 ....................................................................................... 118 Heaters for case 2 ....................................................................................... 119 VOC of MixAlco process in case 2 ......................................................... 120 VOC of CODP in case 2 ............................................................................ 120 FOC of MixAlco and CODP in case 2 .................................................... 121 Summary MixAlco and CODP economic results in case 2 .................... 122 Heat integration comparison of cases......................................................... 124 Economic comparison of cases .................................................................. 124

1. INTRODUCTION

World liquid fuels consumption grew by 0.800 MM bpd in 2012. US Energy Information Administration (EIA) expects consumption growth will be higher over the next two years, at 0.900 million bpd in 2013 and 1.20 MM bpd in 2014 (EIA, 2013). However, the liquid fuel production is estimated to be decline. Furthermore, the price of crude oil is very sensitive to international politic issues. Clearly, new alternatives for renewable fuels are necessary.

The MixAlco technology, invented by Professor M. Holtzapple at Texas A&M University (Holtzapple, 2009), comprises a processing facility to produce liquid transportation fuels and/or value-added chemicals from sustainable resources. MixAlco converts materials such as municipal solid waste (MSW), sewage sludge, forest product residues, and non-edible energy crops such as sweet sorghum into a wide array of chemicals and secondary alcohols that can be further refined through separate, well-established processes to produce renewable gasoline, jet fuel or diesel. The biogasoline produced through the MixAlco technology is not ethanol. In fact, it has a higher energy value than ethanol and can be blended directly with gasoline produced from hydrocarbons. (Terrabon, 2010).

MixAlco process comprises a fermentation stage, which employs a mixed culture of acid-forming microorganisms that convert biomass components (carbohydrates, proteins, and fats) to carboxylate salts. Depending on the choice of buffer, the salts may

be ammonium carboxylates (buffered by NH4HCO3) or calcium carboxylates (buffered by CaCO3) among others. Via pathway C in Figure 1-1, calcium carboxylates are thermally converted into ketones, which are subsequently hydrogenated into a mixture of secondary alcohols. Finally, these alcohols are chemically converted into hydrocarbon fuels (gasoline, jet fuel, and diesel) (Pham, Holtzapple, & El-Halwagi, 2010). In Appendix A, details on the MixAlco process are briefly discussed.

Figure 1-1. Pathways for converting biomass to hydrocarbon fuels (Pham et al., 2010)

Build and run a new plant, such as the one required for the MixAlco process, is very costly; however, its economic performance may be greatly enhanced by retrofitting analysis. This strategy comprises adding a bio-fuels plant like MixAlco process to an existing fossil fuel plant like a crude oil distillation process (CODP).

This mechanism is beneficial for both parties because an inexpensive increase of the production capacity of the refinery may be obtained, while economic matters for the biofuels-producing plant are resolved. The systems obtained by integrating a biomass fuel plant to the fossil fuel plant is regarded here as bio-refineries or integrated fossil bio-refineries.

Basically, CODP comprises a preheating train where crude oil is fed from the holding tank; then vaporized in the furnace where the combustion of a fuel is taking place. Finally, it is fed to the bottom of the distillation column. The distillation column is considered the master unit since all different cuts like light and heavy naphtha, kerosene, light and heavy gas oils, and atmospheric residue are separated and purified. The vacuum distillation unit further distills residual bottoms from the atmospheric tower, where different cuts can be obtained like atmospheric, light vacuum, and heavy vacuum gas oil. A large amount of heat is transported out to the preheating train from the condenser, the end products, the strippers and the pumparounds.

The substantial energy requirement of crude oil distillation columns is met partly by costly utilities, such as steam and fuel for fired heaters, and partly by heat recovered from the process, using process-to-process heat exchange. Energy savings, therefore, demand not only a distillation column that is energy-efficient, but also a heat exchanger network (HEN) which minimizes utility costs by maximizing heat recovery. (Benali & Tondeur, 2011). The CODP in this work corresponds to a modified version of a

distillation unit of Ecopetrol. property rights.

Modifications were necessary to protect intellectual

This work assesses a retrofitting analysis to integrate the MixAlco process to the crude oil distillation process. Focus is given to the problem of process modification to the crude oil distillation system by considering increase the process profitability and material substitution with biomass feedstocks. The approach proposed for this analysis was developed by B. Cormier under the advisory of Dr. M. El-Halwagi at Texas A&M University (Cormier, 2005). The proposed hierarchy is based on costs analysis and involves internal process modification, operating-condition adjustment, and feedstock substitution. If is needed, new units are added followed by the incorporation of new production lines. Then, heat and mass integration techniques are used to link the units and streams. (Cormier, 2005)

The competitiveness of markets nowadays and the focus on energy efficiency requires improved heat-integrated process designs. Aspen Energy Analyzer (AEA) working in concert with flowsheet simulators such as Aspen Plus provides an easy environment to perform optimal heat exchanger network design and pinch analysis. For the economic evaluation, an Aspen Process Economic Analyzer (APEA) provides benefits that will be explored in this study.

2. OBJECTIVES

2.1 General Objective Apply a retrofitting analysis to integrate into a crude oil distillation system, the MixAlco process using the kenitonization route.

2.2 Specific Objectives Conduct process integration studies to determine cost-effective strategies for enhancing production incorporating the MixAlco process into the crude oil distillation system.

Develop several energy and mass integration approaches and use them to induce synergism and to reduce cost by exchanging heat, material utilities, and by sharing equipment.

Develop cost-benefit analysis to guide the decision-making process and to compare various production routes.

3. METHODOLOGY

Results from a previous work on MixAlco process economics were used as a base case (Pham et al., 2012). In that work, the economics of the calcium carboxylate platform (pathway C in Figure 3-1) using municipal solid waste or sugarcane bagasse as feedstock were estimated. On this basis, the following MixAlco process features were used: no requirement for sterility or any external enzymes, low capital cost, and costeffective dewatering, which comprise the use of an effective evaporation system, briefly explained in Appendix A. In the previous work, the minimum selling prices of hydrocarbon fuels reported can be around 1.57 USD /gal if municipal solid waste is available at the US average tipping fee of 45 USD/dry ton (40 ton/h plant, with internal hydrogen production). (Pham et al., 2012)

Retrofitting analysis was performed using the methodology developed by Cormier & El-Halwagi developed on the framework of mass and energy process integration. An overview of the methodology is shown in Figure 3-1 (Cormier, 2005). An explanation is found in Section 3.1.

3.1 Description of the proposed methodology 3.1.1 Define needs

In the first step for the retrofitting analysis, it is possible to define the opportunities in the processes that would result in an increased profitability.

3.1.2

Process arrangements

Figure 3-1 shows three building blocks that are arranged in order of increasing cost. The definition of each block is explained below (Cormier, 2005):

Internal rearrangements: The goal is to reach the production target using low cost strategies. These include process reconfiguration (e.g., stream rerouting) and modification of operating conditions.

Internal modification by adding new units: it is aimed to pursue medium-cost modifications. These include required addition of new units, and/or replacement of the existing units with new ones.

External modification by adding new lines: Capital-intensive strategies are invoked. These include the addition of new production lines.

3.1.3

Feasibility

Once two candidates are integrated into the current plant by heat and mass integration, the ROI can be calculated. The decision to go deeper into the analysis depends on the obtained value. (Cormier, 2005)

Define needs Low Cost Internal rearrangements: Process Reconfiguration Modification of Operating Conditions

Internal rearrangements only

Simulation improvement Cost analysis

Yes Feasible? Internal Modifications: Add New units Modification of Operating Conditions Medium Cost Internal modification by adding new units

Simulation improvement Cost analysis

Redefine needs

Yes Feasible?

Proposal to the company

High Cost External modification by adding separated lines External Modifications: Add new lines Modification of Operating Conditions

Simulation improvement Cost analysis

Yes Feasible?

Figure 3-1. Flowchart of the proposed methodology (Cormier, 2005).

3.2 Simulation Tools Regardless to existence of specialized software for petroleum industry (Aspen Hysys and PRO II), Aspen Plus software was used according a specific database that estimates most of the desired properties of biomass. Initially, each one of these two base cases was simulated separately. Then, both plants were put together in a single worksheet to make integrations possible. Specificities of each of these simulation cases are given below. For all simulations, the following three steps were necessary: Flow sheet definition: All inlet and outlet streams to the different stages in both the MixAlco and the CODP systems, as well as all unit operations and their interconnecting streams were defined. Chemical components: All chemical components in the system, from reagents to intermediates and products were specified during simulations. Appendix B shows the properties for each of the substances used in the simulations.. Operating conditions: The operating conditions, such as temperature, pressure, heat duties etc., for each unit operation were specified for each process in next sections. 3.2.1 MixAlco process base case.

The simulation was made using the National Renewable Energy Laboratory (NREL) database In-house Pure Component Database (INHSPCD). Within this tool,

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estimation of most of the properties of biomass components such as glucose, xylose, cellulose, xylan, lignin were possible. Components other than the ones listed above, are identified within this database as solslds. (Wooley & Putsche, 1996). As Wooley and Putsche, (1996) suggested, the thermodynamic package used in this simulation was non-random-two-liquid (NTRL), where NRTL liquid include activity coefficient model, Henrys law for the dissolved gases, and Redlich-KwongSoave (RKS) equation of state for the vapor phase. The MixAlco process simulation was made for a capacity of 40.0 ton/h of biomass. The biomass feedstock in the simulation was a mixture 80.0% - 20.0% w/w of sugarcane bagasse (like carbohydrate source) and chicken manure (like secondary nutrient source) respectively. Table 3-1 shows the biomass feed composition. Other details on the feedstock stream (e.g., properties) are shown with simulation results in Section 4.1.1.1. Table 3-1. Biomass feed composition for MixAlco process Component Cellulose Hemicellulose (xylan) Lignin Solslds Total ton/h 16.8 7.50 10.0 5.20 40.0 Feedstock %w/w 43.0 19.0 25.0 13.0 100

Operating conditions used for simulation of all MixAlco unit operations are shown in Table 3-2.

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Table 3-2. MixAlco operating conditions Process Feed handling Pretreatment Fermentation Ketonization Ketone hydrogenation Lime kiln Alcohol dehydration Oligomerization Olefin hydrogenation Gasification Steam-gas shift Parameter Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Temperature (C) Pressure (bar_a) Value 55.0 1.00 55.0 1.00 55.0 1.00 430 0.0400 130 55.0 500 1.00 300 3.00 300 3.00 130 55.0 760 1.00 254 1.00

3.2.2

CODP base case.

The CODP simulation was made using Grayson Streed and Braun k-10 (BK10) as thermodynamic packages, for a crude oil load of 27,012 bpd (162 ton/h) and 22.8 API. Because, Grayson property methods were developed for systems containing hydrocarbons and light gases and BK10 property method is suited for vacuum and low pressure applications. (Aspen plus, 2013). Table 3-3 and 3-4 shows the assay data. The crude oil distillation curve is presented in Figure 3-2.

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Table 3-3. Assay data for crude oil****

%Distilled* 0.929 2.54 5.46 8.71 11.5 13.7 16.6 21.9 28.8 36.6 41.3 44.9 53.8 62.1 67.3 85.0 Molecular Weight 71.0 97.0 116 144 153 171 186 206 250 280 323 357 378 436 514 1,247 Molecular weight: 288 Specific Gravity 0.646 0.725 0.759 0.788 0.810 0.823 0.838 0.862 0.872 0.897 0.920 0.921 0.932 0.946 0.956 1.03 Sulfur curve** Viscosity*** (80C) Viscosity*** (100C)

5x10-3 0.0190 0.0500 0.0790 0.322 0.808 0.995 1.19 1.42 Bulk value: 0.0488 9.13 10.3 18.0 43.3 77.8 289,150 5.80 5.79 10.3 22.5 34.5 31,971

*Mid-percent distilled (same basis as distillation data, i.e., volume or weight) **Given in %w/w ***Given in centistokes ****Data supply by Ecopetrol

Table 3-4. Assay data for crude oil Light ends**

Component* C2 C3 IC4 NC4 IC5 NC5 Hexane Total % light ends in the assay % Mass 0.212 3.60 5.40 14.5 24.4 23.5 28.4 0.940

*The number after C refers to the number of carbons in the alkane molecule. I is for iso (non-linear) structures and N for straight chains **Data supply by Ecopetrol

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Figure 3-2. Crude oil distillation TPB

Operating conditions used for the atmospheric and vacuum columns are shown in Table 3-5. Table 3-5. CODP operating conditions Process Parameter Column T-204 - Atmospheric tower Heat duty condenser (kJ/s) Tray crude feed Tray steam feed Tray number Condenser Temperature tray 1 (C) Temperature tray 19 (C) Pressure tray 1 (bar_a) Pressure tray 19 (bar_a) Heat duty pumparound MPA (kJ/s) Heat duty pumparound MPACAL (kJ/s) Column T-205- Vaccum tower Heat duty condenser (kJ/s) Tray crude feed Tray steam feed Tray number Value 7,206 17.0 19.0 19.0 Partial 98.0 366 1.70 2.20 5,113 563 308 7.00 8.00 8.00

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Process

Parameter Condenser Temperature tray 1 (C) Temperature tray 8 (C) Pressure tray 1 (bar_a) Pressure tray 8 (bar_a) Heat duty pumparound UPA (kJ/s) Heat duty pumparound MPA (kJ/s) Heat duty pumparound MPACAL (kJ/s)

Value Partial 60.0 389 0.0400 0.140 2,117 5,874 219

3.2.3

MixAlco process and CODP retrofitted plant

The simulation of MixAlco process and CODP integrated was made from the base case of each plant, so the operating conditions and feedstock properties were the same shown in sections 3.2.1 and 3.2.2; regarding the thermodynamic package: NTRL and Grayson Streed. 3.3 Process integration The design of any industrial process relies on process simulators and programs for unit operation design. The core of process design rests on two important dimensions: mass and energy. Mass involves the creation and routing of chemical species in reaction, separation, and byproduct/waste-processing systems. These constitute the heart of the process and define a companys technology base. Energy provides the necessary heating, cooling, and shaftwork for those systems. Because most industrial processes are complicated, performance and economics depend not only on proper selection and design of individual components but also on

15

proper assembling of building blocks. Fundamental principles can guide this assembly. Process integration comprises all means to achieve the goals of optimal assembly and performance. In process integration, the unity of the entire process is emphasized.

Pinch analysis is the most successful way to achieve energy integration; which impacts mainly in process economics. Mass integration, on the other hand, has received great attention and development, because it directly impacts process performance. (ElHalwagi & Spriggs, 1998). For this, material rerouting and heat exchanger network (HEN) were considered (Cormier, 2005). 3.3.1. Material rerouting Mass integration is a systematic methodology that provides a fundamental understanding of the global flow of mass within the process and employs this understanding. To apply this integration the following steps were used: Analysis: Detect the minimum fresh resource consumption and minimum waste discharge streams.

Retrofit: Modify an existing water-using network to maximize water reuse and minimize wastewater generation through effective process changes (Cormier, 2005). For additional details about this type of integration see Appendix C.

16

3.3.2 Heat Exchanger Network (HEN) In the plant, heating and cooling represent an important operating cost. In order to minimize the operating cost for the heat utilities, heat integration is needed. The following multiple design objectives are pursued: Minimize the investment cost of the units (i.e., surface area of exchanger, heater and/or cooler).

Minimize the operating cost of utilities (steam, cooling water, etc).

Minimize the number of units (i.e., heat exchanger). (Cormier, 2005) In this work, energy integration was performed using Aspen Energy Analyzer (AEA) in compliance to all license agreements. For additional details about this type of integration see Appendix D. 3.3.3 Cost Analysis Many technical and environmental decisions during process design are strongly impacted by economic factors; therefore, an essential component of any sustainable design is an economic analysis, which is performed on the basis of total investment and operating costs. (El-Halwagi, 2012). Typically, a minimum of 15.0% for the ROI is pursued. If this is not achievable, ROIs of 5.00 to 10.0% may be acceptable under

17

current market conditions. (Cormier, 2005) Additional details about economic analysis concepts are presented in Appendix E. In this work, the prices for feedstocks, chemicals and material disposal for MixAlco process were taken from Pham et al., (2012). The prices of crude oil were taken from the EIA official website. The utilities costs were taken from the database of AEA except for the steam cost, which was taken from Seider, (2004). Finally, the prices for refinery products were found in the EIA official website. Appendix D shows the price profile for these products. For Atmospheric Gas Oil (AGO) and Light Vacuum Gas Oil (LVGO) prices, a factor of 10% from the price of Heavy Vacuum Gas Oil (HVGO) was used. All these prices are shown in Table 3-6. Table 3-6. Feedstock, utilities and product prices Item Sugarcane bagasse (USD/ton) Chicken manure (USD/ton) Crude oil (USD/ton) Crude oil (USD/barrel) Quick Lime (USD/ton) Flocculant (USD/ton) Iodoform (USD/kg) CaCO3 (USD/ton) Material disposal (USD/ton) Fired Heat (USD/ton) MP Steam (USD/ton) Cooling Water (USD/m3) LP Steam (USD/ton) Refrigerant (USD/m3) Electricity (USD/kWh) Steam @ 353C (USD/ton) Steam @ 454C (USD/ton) Costs and Prices (USD / unit) 60.0 10.0 643 93.4 70.0 991 25.0 50.0 18.0 2.55 4.36 4x10-3 4.17 0.0130 0.0620 10.0 10.0

Utilities cost

Feedstock costs

18

Item Gasoline (USD/gal) Jet (USD/gal) Diesel (USD/gal) AGO (USD/gal) LVGO (USD/gal) HVGO (USD/gal) Asphalt (USD/gal)

Costs and Prices (USD / unit) 3.28 2.88 3.75 2.40 2.30 2.20 1.30

Products selling prices

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RESULTS AND DISCUSSION

Simulation results are presented for each one of the two base cases (MixAlco and COPD). This simulations were necessary in order to be able to compare MixAlco alone vs MixAlco retrofitted within a COPD plant. Then, the methodology for retrofitting (shown in Figure 3-1) will be followed, which eventually (third loop) conduces to the results obtained for the combined MixAlco-COPD integrated plant. An economic analysis is presented for each one of the integration possibilities and for the combined MixAlco-COPD. Extensive comparisons are presented at the end. The Enthalpy reported by Aspen Plus is in their standard states at 1 atm and 298.15K. 4.1 Simulation results In this section, simulation building procedures as well as relevant results of each one of the base cases are discussed next (MixAlco base case and COPD base case). 4.1.1 Simulation builds up and results for MixAlco base case The MixAlco simulation was divided in seven blocks to build up a simulation, as shown in Figure 4-1. These blocks are listed and explained below: 1. FEED-HAN: Feed handling process 2. PRET -FER: Pretreatment and fermentation process 3. DEWATER: Dewatering process. 4. KETONIZA: Ketonization and ketone hydrogenation processes.

20

5. LIME-KIL: Lime kiln process. 6. FINAL: Dehydratation, oligomerization and saturation processes. 7. GASIFICA: Gasification reactor, steam gas shift reactor, and adsorption process

Figure 4-1. Blocks of MixAlco process simulation

21

4.1.1.1 MixAlco Block description Feed Handling (Unit 1)

The Feed Handling block exists only for simulation purposes and it is meant: (i) to mix the reacting substances (biomass, water, and lime) to prepare them for pretreatment and (ii) to obtain lime (Ca(OH)2) from quick lime (CaO) as shown in Equation 4-1.

(4-1) Quick lime Lime

In the actual MixAlco process, feed handling would occur simultaneously (in the same unit) with pretreatment. This is because the reaction in Eq. 4-1 is exothermic (Enthalpy of reaction obtained was 1.960kJ/s shown in Table 4-2); thus, it is advantageous to use the reaction heat to obtain an increase of temperature necessary for pretreatment to occur at a measurable rate. Because in the simulation feed handling and pretreatment were not put in the same unit, this fact could not be considered. Instead, an external source of heat was implemented for the pretreatment stage.

Two sources for quick lime were considered: The first is CaO produced in-site and the second is make-up fresh quick lime. The quick lime that is produced in site comes from the LIME-KIL block explained in a later section. The stream that carries this reactant has been labeled as CAO-RECY in Figure 4-2. As shown in Table 4-1, this stream contains 4.06 ton/h of CO2 which corresponds to 44.0% w/w of the stream composition. This gas is

22

a reaction byproduct which in the actual process is expelled as it is produced, but in this simulation has to be carried all the way to the end gasification block in the SP-115. The unit operation CON-101 is a conveyor set up to transport this recycled stream. On the other hand, the fresh, make-up CaO (labeled as CAO-MAKE in Figure 4-2) is purchased with a cost of 70.0USD/ton. The mass ratio CAO:CAO-MAKE is 1:10 which clearly shows that a lime recovery process is represented in a saving operating cost. In addition a water fed at a flow rate of 2ton/h, stream labeled as H2O-LIME in Figure 4-2 was considered.

For the reaction (Eq. 4-1, occurring in R-101), a conversion factor of 1 was employed, although the reactants (i.e., water and quick lime) were fed in exact stoichiometric amounts (i.e., no reactant was fed in excess). (Gosseaume, 2011).

Two streams leave this block: (i) Stream 1(OUT) in Figure 4-2 required for the reactor convergence and after a mixing unit (TK-101) (ii) Stream (BIOM-LIM(OUT)) which is the stream that contains biomass mixed with water and lime and goes to pretreatment.

Results from mass and heat balance in the simulation for this block are shown per stream in Table 4-1. On the other hand, the heat balance for the equipment in this block is shown in Table 4-2, where the conveyor power consumption is very low.

23

Figure 4-2. Feed handling simulation

24

Table 4-1. Feed handling mass and heat balance BIOMASS Temperature (C) 25.0 Pressure (bar_a) 1.00 Mass vapor fraction 0 Mass solid fraction 0.870 Mass flow (ton/h) 39.5 80,720 Enthalpy (kJ/s) Component mass flow (ton/h) CELLU-01 16.8 XYLAN 7.50 LIGNI-01 10.0 SOLSL-01 5.17 SOLUN-01 0 WATER 0 CO2 0 CA(OH)2 0 CAO 0 CA-BIO 55.0 1.00 0.0800 0.820 51.6 120,205 16.8 7.50 10.0 5.17 0 0.0500 4.06 8.03 0 CA-BIOM 55.0 1.00 0.0800 0.820 51.6 120,205 16.8 7.50 10.0 5.17 0 0.0500 4.06 8.03 0 CAO 55.0 1.00 0.440 0.560 9.24 26,310 0 0 0 0 0 0 4.06 0 5.18 CAO-MAKE CAO-RECY 55.0 55.0 1.00 1.00 0 0.440 1.00 0.560 0.900 9.24 2,824 26,310 0 0 0 0 0 0 0 0 0.900 0 0 0 0 0 0 4.06 0 5.18 H20-LIME 25.0 1.00 0 0 2.00 8,809 0 0 0 0 0 2.00 0 0 0

Table 4-2. Heat balances for Feed Handling equipment Type Reactor Conveyor Unit R-101 CON-101 Heat duty [kJ/sec] -1,541 0.750 Heat duty [kJ/h] -5.55x106 2.7 x103

25

Pretreatment and Fermentation (Unit 2)

Lignocellulosic materials are resistant to the enzymatic degradation, because cellulose and hemicelluloses (carbohydrates) are encapsulated by lignin, which keeps the enzymes secreted by the microorganisms from reaching it. Pretreatment is necessary to remove lignin and enable the fermentation step. (Gosseaume, 2011). The pretreatment simulation is shown in Figure 4-3. For pretreatment conditions 400 ton/h of fresh water stream (labeled as H2O-PRET in Figure 4-3) was required. Also a blower (CM-101) was simulated for bring the air in the pretreatment slurry (6.70ton/h).

Figure 4-3. Pretreatment simulation

26

Due to the complex reaction in pretreatment stage, the reactor R-102 was simulated in two ways: (i) the first way (for mass balance) was through Ryield, based on known yield of the exit current. And (ii) the second way (for heat balance) was through Rstoic in order to calculate the endothermic heat of reaction that was 14,044kJ/s shown in Table 4-5. For the Rstoic reactor was assumed a conversion factor of 15.0% (Eq. 4-2), 35.0% (Eq. 4-3) and 30.0% (Eq. 4-4) for cellulose, xylan and lignin in the undigested biomass (Mixed), respectively (Sierra, Garca, & Holtzapple, 2010). These conversions were based on a study of lime pretreatment of poplar wood at laboratory scale. Based on previous studies of MixAlco process at different capacities as Holtzapple, (2004), it is assumed that yields are not affected by the scaling capacity. The biomass undigested conversion is 0.200 ton per ton of biomass VS, (in stream BIOM-LVS, 34.9 ton/h is biomass VS) resulting in 8.80 ton/h of undigested biomass, that is directed to gasification process (labeled as BIOM-LV in Figure 4-3). The remaining biomass is digested (Cisolid) (labeled as BIOM-S in Figure 4-3) and continued to fermentation process. In this stream the theorical conversion of 0.800 ton of digested biomass per ton of biomass VS is satisfied, resulting in 26.1 ton/h. CELLU-01(Cisolid) --> CELLU-01(Mixed) (4-2) XYLAN (Cisolid) --> XYLAN (Mixed) LIGNI-01(Cisolid) --> LIGNI-01(Mixed) (4-3) (4-4)

In fermentation process the biomass digested (labeled as BIOM-LV in Figure 4-3 and 4-4) is converted in carboxylates salts using as a buffer CaCO3. The fermentation simulation is shown in Figure 4-4.

27

Table 4-3. Pretreatment mass and heat balance AIR 25.0 1.00 1.00 0 6.70 3.46x10-13 0 0 0 0 0 0 0 5.30 1.40 AIR2 30.5 1.00 1.00 0 6.70 10.4 0 0 0 0 0 0 0 5.30 1.40 AIRR 30.5 1.00 1.00 0 6.70 10.4 0 0 0 0 0 0 0 5.30 1.40 BIOM-LIM BIOM-LV BIOM-LVS 55.0 55.0 55.0 1.00 1.00 1.00 0.0770 0 0 0.820 0.0200 0.0760 51.6 416 442 120,205 1,854,269 1,910,655 16.8 7.50 10.0 5.2 0.0 4.10 8.00 0 0 2.80 2.80 3.20 5.00 402 0 0 0 0 17.0 7.80 10.1 5.00 402 0 0 0 0 BIOM-S 55.0 1.00 0 1.00 26.1 56,386 14.2 5.00 6.90 0 0 0 0 0 0 H20-PRET 25.0 1.00 0 0 400 1,761,927 0.0 0.0 0.0 0 400 0 0 0 0

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) CELLU-01 XYLAN LIGNI-01 SOLSL-01 WATER CO2 CA(OH)2 NITROGEN O2

Two sources for calcium carbonate were considered: The first is CaCO3 recycled from KETONIZA block and the second is make-up fresh CaCO3. The flow rate of CaCO3 recycled is 6.30 ton/h as shown in Table 4-4; this stream is labeled as CACO3REC in Figure 4-4. The make-up flow rate is 9.30 ton/h (labeled as MK-CACO3 in Figure 4-4) and is purchased with a cost of 50.0 USD/ton. The CaCO3 recycled represent 40.0% of CaCO3 consumption resulting in a saving operating cost.

28

The conversion factors for the serial reactions performed in the fermentation train (R-103 to R-105) are shown in Table A-1 (Gosseaume, 2011). Besides, the reactions in fermentation process are shown in Equations A-1 to A-11. The salts in solution are obtained in the stream called SALTS shown in Figure 4-4, with a total flow rate of 25.1 ton/h as shown in Table 4-4. A theorical conversion is getting for 0.600 ton of carboxylate salts per ton of biomass feed. The stream residue from fermentation (BIOMASS) with a flow of 16.1 ton/h goes to a gasification process. Table 4-4 shows the material balance for this stage. In addition a water fed at a flow rate of 200 ton/h, stream labeled as H2O-FERM in Figure 4-4 was considered. The global heats of reaction are exothermic for reactor R103, R-104, R-105 (with enthalpies 1,051kJ/s; 768 kJ/s; 278kJ/s respectively); and endothermic for reactor R-106 (with enthalpy 6,480kJ/s). Table 4-5 shows the summary of heat equipment loads. Finally, a water cooling circuit is simulated in order to quantify the cost of those equipment for improve the cost analysis of this process.

Results from mass and heat simulation for this block are shown per stream in Table 4-4. On the other hand, heat balances for this block shows a power consumption of 40.4kW (Table 4-5). For a heat integration study the heat exchangers simulated in this block were assumed as coolers for count the cooling water utility in the operating cost, that why the total cooling required in this block is 7,957 kJ/s.

29

Figure 4-4. Fermentation simulation

30

Table 4-41. Fermentation mass and heat balance

BIO-SAL 55.0 1.01 0 0.177 247.6 -991,492 8.80 3.10 6.90 200.5 3.20 0 1.30 19.2 1.40 3.30 BIO-SAL1 55.0 1.01 0.0100 0.129 236.4 970,009 4.60 1.60 6.90 200.3 5.70 0 3.20 11.4 1.00 1.80 BIO-SAL2 55.0 1.01 0.0170 0.0890 227.5 951,047 2.20 0.80 6.90 200.1 7.10 0 3.90 5.40 0.30 0.90 BIO-SAL3 55.0 1.01 0.0210 0.0590 220.9 934,782 1.00 0.400 6.90 200.1 7.80 0 2.50 1.90 0.100 0.200 BIOM1 55.0 1.01 0.147 0.853 22.0 52,274 8.80 3.10 6.90 0 3.20 0 0 0 0 0 BIOM2 55.0 1.01 0.302 0.698 18.8 49.090 4.60 1.60 6.90 0 5.70 0 0 0 0 0 BIOM3 55.0 1.01 0.418 0.582 17.0 47,282 2.20 0.800 6.90 0 7.10 0 0 0 0 0 BIOMASS 55.0 1.01 0.486 0.514 16.1 46,334 1.00 0.400 6.90 0 7.80 0 0 0 0 0

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Entalphy (kJ/s) Component mass flow (ton/h) CELLU-01 XYLAN LIGNI-01 WATER CO2 CA(OH)2 CACO3 CA(CH-01 CA(CH-02 CA(CH-03

(Continued Table 4-4)

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) CACO3 55.0 1.00 0 1.00 6.30 CACO3-1 37.3 1.00 0 1.00 3.90 CACO3-2 37.3 1.00 0 1.00 3.90 CACO3-4 37.3 1.00 0 1.00 3.90 CACO3-5 37.3 1.00 0 1.00 3.90 CACO3REC 130 7.60 0 1.00 6.30 CW-1 CW2 25.0 31.1 1.00 0.800 0 0 0 0 301.8 301.8 CW3 25.0 1.00 0 0 301.8 CW4 31.1 0.800 0 0 301.8

31

Entalphy (kJ/s) Component mass flow (ton/h) CELLU-01 XYLAN LIGNI-01 WATER CO2 CA(OH)2 CACO3 CA(CH-01 CA(CH-02 CA(CH-03

CACO3 21,066 0 0 0 0 0 0 6.30 0 0 0

CACO3-1 13,018 0 0 0 0 0 0 3.90 0 0 0

CACO3-2 13,018 0 0 0 0 0 0 3.90 0 0 0

CACO3-4 13,018 0 0 0 0 0 0 3.90 0 0 0

CACO3-5 13,018 0 0 0 0 0 0 3.90 0 0 0

CACO3REC 20,949 0 0 0 0 0 0 6.30 0 0 0

CW-1 CW2 CW3 1.33x106 0 0 0 301.8 0 0 0 0 0 0 0 0 0 301.8 0 0 0 0 0 0 0 0 0 301.8 0 0 0 0 0 0

CW4

0 0 0 301.8 0 0 0 0 0 0

(Continued Table 4-4)

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Entalphy (kJ/s) Component mass flow (ton/h) 0 CELLU-01 0 XYLAN 0 LIGNI-01 SOLSL-01 0 302 WATER CW5 25.0 1.00 0 0 302 CW6 31.1 0.800 0 0 302 CW6 CW7 31.1 25 0.800 1.00 0 0 0 0 302 302 1.33x106 0 0 0 0 302 0 0 0 0 302 CW8 31.1 0.800 0 0 302 H2O H20-FERM H20-PRET MK-CACO3 SAL-H2O SALT3 41.1 50.0 25.0 25.0 55.0 55.0 0.800 1.00 1.00 1.00 2.06 1.01 0 0 0 0 0 0 0 0 0 1.00 0.112 0.0800 200 200 400.0 9.30 225.6 217.6 877,480 875,520 1,761,927 31,006 939,210 921,027 0 0 0 0 200 0 0 0 0 200 0 0 0 0 400 0 0 0 0 0 0 0 0 0 200 0 0 0 0 200

0 0 0 0 302

0 0 0 0 302

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CO2 CA(OH)2 CACO3 CA(CH-01 CA(CH-02 CA(CH-03

CW5 0 0 0 0 0 0

CW6 0 0 0 0 0 0

CW6 0 0 0 0 0 0

CW7 0 0 0 0 0 0

CW8 0 0 0 0 0 0

H2O 0 0 0 0 0 0

H20-FERM H20-PRET MK-CACO3 SAL-H2O SALT3 0 0 0 0 0 0 0 0 0 0 0 0 9.30 1.30 3.20 0 0 0 19.2 11.4 0 0 0 1.40 1.00 0 0 0 3.30 1.80

(Continued Table 4-4) Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Entalphy (kJ/s) Component mass flow (ton/h) CELLU-01 XYLAN LIGNI-01 SOLSL-01 WATER CO2 CA(OH)2 CACO3 CA(CH-01 CA(CH-02 CA(CH-03 SALT4 55.0 1.01 0 0.0490 210 903,943 0 0 0 0 200 0 0 3.90 5.40 0.300 0.900 SALT5 55.0 1.01 0 0.0230 205 888,661 0 0 0 0 200 0 0 2.50 1.90 0.100 0.200 SALTS 55.0 1.01 0 0.112 226 939,217 0 0 0 0 200 0 0 1.30 19.2 1.40 3.30 SALW1 46.3 1.86 0 0.0800 218 922,979 0 0 0 0 200 0 0 3.20 11.4 1.00 1.80 SALW2 55.0 2.06 0 0.0800 218 921,020 0 0 0 0 200 0 0 3.20 11.4 1.00 1.80 SALW3 46.3 1.86 0 0.0490 210 905,896 0 0 0 0 200 0 0 3.90 5.40 0.300 0.900 SALW4 55.0 2.06 0 0.0490 210 903,936 0 0 0 0 200 0 0 3.90 5.40 0.300 0.900 SALW5 46.3 1.86 0 0.0230 205 890,613 0 0 0 0 200 0 0 2.50 1.90 0.100 0.200 SALW6 55.0 2.06 0 0.0230 205 888,653 0 0 0 0 200 0 0 2.50 1.90 0.100 0.200

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Table 4-5. Heat balances for Pretreatment and Fermentation equipments Type Cooler Heat Exchanger Heat Exchanger Heat Exchanger Heat Exchanger Pumps Pumps Pumps Pumps Compresor Reactor Reactor Reactor Reactor Reactor Unit C-101 E-101 E-102 E-103 E-104 P-101 P-102 P-103 P-104 CM-101 R-102 R-103 R-104 R-105 R-106 Heat duty [kJ/sec] 117 1,960 1,960 1,960 1,960 7.50 7.50 7.50 7.60 10.4 14,044 -1,051 -768 -278 6,480 Heat duty [kJ/h] 4.21x105 7.06x106 7.06x106 7.06x106 7.06x106 2.70x104 2.70x104 2.70x104 2.70x104 3.74x104 5.06x107 -3.78x106 -2.76x106 -1.00x106 2.33x107

Dewatering (Unit 3)

Dewatering block exits only for simulated the water separation from the produced fermentation broth, using a vapor compression. Figure 4-5 shows the block simulation. The fermentation broth labeled as SALT-H20 comes 25.1 ton/h of salt plus 200 ton/h of water. A six train of heat exchangers and separators are used to simulate the vapor compression system, where the steam separated in the first train is compressed for recycling in the process. The separated water (labeled as WATDISTI in Figure 4-5) is a waste water stream. The separated salts labeled as SALTDES continued to ketonization process. Others packing units are simulated in order to quantify the cost of that equipment for improve the cost analysis of this block.

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Results from mass and heat simulation for this block are shown per stream in Table 4-6. On the other hand, heat balances for this block shows power consumption for compressor CM-102 of 1,214 kW. A heating load required in this block is 113,763 kJ/s (Table 4-7)

Figure 4-5. Dewatering simulation

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Table 4-62. Dewatering mass and heat balance

SAL-DESC SAL-H20 55.0 55.0 2.06 2.06 0 0 0.112 0.112 225.6 225.6 939,210 200 1.30 19.2 1.40 3.30 939,210 200 1.30 19.2 1.40 3.30 SAL1 162 6.00 0 1.00 4.20 10,431 0 0.200 3.20 0.200 0.500 SAL2 162 6.50 0 1.00 4.20 10,431 0 0.200 3.20 0.200 0.500 SAL3 163 6.60 0 1.00 4.20 10,431 0 0.200 3.20 0.200 0.500 SAL4 165 6.90 0 1.00 4.20 10,431 0 0.200 3.20 0.200 0.500 SAL5 165 7.00 0 1.00 4.20 10,431 0 0.200 3.20 0.200 0.500 SAL6 162 6.50 0 1.00 4.20 10,431 0 0.200 3.20 0.200 0.500 SALT 163 6.00 0 1.00 25.2 62,572 0 1.30 19.2 1.40 3.30 SALT-H20 150 1.90 0.900 0.100 225.6 796,918 200 1.30 19.2 1.40 3.30 SALTWAT 55.0 2.10 0 0.100 225.6 939,210 200 1.30 19.2 1.40 3.30

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) WATER CACO3 CA(CH-01 CA(CH-02 CA(CH-03

(Continued Table 4-6)

SALTDE SALWR SALWR SALWR SALWR SALWR SALWR SALWR SALWR SALWR SALWR1 SALWR1 S 1 2 3 4 5 6 7 8 9 0 1 Temperature (C) 163 150 150 150 150 150 150 165 165 165 165 165 Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Enthalpy (kJ/s) 6.00 0 1.00 25.2 62,572 1.90 0.900 0.100 37.6 132,846 1.90 0.900 0.100 37.6 132,846 1.90 0.900 0.100 37.6 132,846 1.90 0.900 0.100 37.6 132,846 1.90 0.900 0.100 37.6 132,846 1.90 0.900 0.100 37.6 132,846 7.00 0 0.100 37.6 132,846 7.00 0 0.100 37.6 132,846 7.10 0 0.100 37.6 132,846 7.40 0 0.100 37.6 132,846 7.50 0 0.100 37.6 132,846

36

SALTDE SALWR SALWR SALWR SALWR SALWR SALWR SALWR SALWR SALWR SALWR1 SALWR1 S 1 2 3 4 5 6 7 8 9 0 1 Component mass flow (ton/h) WATER CACO3 CA(CH-01 CA(CH-02 CA(CH-03 0 1.30 19.2 1.40 3.30 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500 33.4 0.200 3.20 0.200 0.500

(Continued Table 4-6)

SALWR12 SALWR13 SALWR14 SALWR15 SALWR16 SALWR17 SALWR18 Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Enthalpy (kJ/s) WATER CACO3 CA(CH-01 CA(CH-02 CA(CH-03 164 7.00 0 0.100 37.6 151,669 33.4 0.200 3.20 0.200 0.500 162 6.50 0.1 0.100 37.6 150,843 33.4 0.200 3.20 0.200 0.500 162 6.50 0 0.100 37.6 151,649 33.4 0.200 3.20 0.200 0.500 163 6.60 0 0.100 37.6 151,649 33.4 0.200 3.20 0.200 0.500 165 6.90 0 0.100 37.6 151,649 33.4 0.200 3.20 0.200 0.500 165 7.00 0 0.100 37.6 151,649 33.4 0.200 3.20 0.200 0.500 162 6.50 0 0.100 37.6 151,649 33.4 0.200 3.20 0.200 0.500 ST2 177 9.30 1 0 33.4 ST3 175 8.80 1 0 33.4 ST4 172 8.30 1.00 0 ST5 170 7.80 1.00 0

33.4 33.4 121,929 121,971 122,015 122,061 33.4 0 0 0 0 33.4 0 0 0 0 33.4 0 0 0 0 33.4 0 0 0 0

Component mass flow (ton/h)

37

(Continued Table 4-6)

ST6 167 7.30 1.00 0 ST7 166 7.10 1.00 0 STEAMM WAT1 230 163 9.80 6.00 1.00 1.00 0 0 33.4 120,971 33.4 0 0 0 0 WAT6 WATDISTI WATER 162 60.0 162 6.50 5.50 6.50 1.00 0 1.00 0 0 0 33.4 33.4 33.4 33.4 33.4 33.4 200 200 875,450 733,155 122,185 122,193 122,185 122,185 122,185 122,185 33.4 0 0 0 0 33.4 0 0 0 0 33.4 0 0 0 0 33.4 0 0 0 0 33.4 0 0 0 0 33.4 0 0 0 0 200 0 0 0 0 200 0 0 0 0 WAT2 162 6.50 1.00 0 WAT3 163 6.60 1.00 0 WAT4 164 6.90 0.0 0 WAT5 165 7.00 1.00 0

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) 33.4 33.4 122,110 122,130 Enthalpy (kJ/s) Component mass flow (ton/h) WATER 33.4 33.4 CACO3 0 0 CA(CH-01 0 0 CA(CH-02 0 0 CA(CH-03 0 0

Ketonization (Unit 4)

Ketonization simulation is shown in Figure 4-6; and Table 4-8 shows the material balance. In ketonization block the carboxylate salts (labeled as SALDEH in Figure 4-6) are converted into ketones (labeled as KET-CACO in Figure 4-6) by a thermal conversion at high temperatures (430C), and vacuum pressure (30 mmHg); producing 9.60 ton/h of ketones. The conversion factor for the serial reactions performed in the reactor R-107 was 0.99 (Gosseaume, 2011). The reactions in ketonization are shown in Equations A-12 to A-16 (Appendix A).

38

Table 4-7. Heat balances for Dewatering equipments Type Heater Heater Heater Heater Heater Heater Heat Exchanger Heat Exchanger Heat Exchanger Heat Exchanger Heat Exchanger Heat Exchanger Heat Exchanger Compressor Unit H-101 H-102 H-103 H-104 H-105 H-106 E-105 E-106 E-107 E-108 E-109 E-110 E-111 CM-102 Heat duty [kJ/sec] 18,956 18,956 18,956 18,956 18,956 18,983 142,292 958 42.0 44.0 46.0 48.0 20.0 1,214 Heat duty [kJ/h] 6.82x107 6.82x107 6.82x107 6.82x107 6.82x107 6.83x107 5.12x108 3.45x106 1.51x105 1.58x105 1.66x105 1.73x105 7.20x104 4.37x106

By the thermal conversion 14.2 ton/h of calcium carbonate was produced. The carbonate produced (labeled as CACO3 in Figure 4-6) leaves this block to a LIME-KIL block explained in the next section. Followed by ketonization, a ketone hydrogenation process continued to produce alcohols. In reactor R-108 the conversion factor for serial reactions was 1 (Gosseaume, 2011). The equations for hydrogenation are shown in (Appendix A) Eq. A-17 to A-22. The hydrogenation conditions are high pressure (55 bar) and isothermal (130C). The net demand of hydrogen is 0.0290 ton H2/ton mixed alcohol, and it is produced in gasification block explained in last section.

39

The reaction for R-107 is endothermic with enthalpy 4,580kJ/s, but the reaction for R-108 is exothermic with enthalpy -2,615 kJ/s, then heat integration is possible to study. Table 4-9 shows the summary of heat equipment loads. On the other hand, heat balances for this block shows a power consumption of 1,309 kW for pumps and compressor (Table 4-9). The cooling demand in this block is 4,792kJ/s and the heating demand is 4,003 kJ/s.

Figure 4-6. Ketonization simulation Table 4-8. Ketonization mass and heat balance
ALCOHOL CACO3 H2 H2-1 H21 KET KET-CACO KETO KETONES

40

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) CACO3 CA(CH-03) HYDROGEN ACETONE BUTANONE HEXANONE PENTANON HEPTANON NONANONE ISOPROPANOL BUTANOL HEXANOL PENTANOL HEPTANOL NONANOL

ALCOHOL CACO3 130 130 55.0 7.60 0.0190 0 3x10-3 1.00 10 15.5 12,226 51,675 0 0.0300 0.0500 0 0 0 0 0 0 7.20 0.180 2x10-3 0.560 0.0100 1.90 15.5 0 0 0 0 0 0 0 0 0 0 0 0 0 0

H2 43 0.900 1.00 0 0.340 24 0 0 0.340 0 0 0 0 0 0 0 0 0 0 0 0

H2-1 130 54.8 1.00 0 0.340 142 0 0 0.340 0 0 0 0 0 0 0 0 0 0 0 0

H21 961 55.0 1.00 0 0.340 1,640 0 0 0.340 0 0 0 0 0 0 0 0 0 0 0 0

KET 130 7.60 0 0.619 25.2 61,455 15.5 0.0300 0 7.00 0.200 0 0.500 0 1.90 0 0 0 0 0 0

KET-CACO 430 0.0400 0.38 0.619 25.2 57,409 15.5 0.0300 0 7.00 0.200 0 0.500 0 1.90 0 0 0 0 0 0

KETO 133 55.0 0 3x10-3 9.6 9,754 0 0.0300 0 7.00 0.200 0 0.500 0 1.90 0 0 0 0 0 0

KETONES 130 7.60 0 3x10-3 9.6 9,779 0 0.0300 0 7.00 0.200 0 0.500 0 1.90 0 0 0 0 0 0

(Continued Table 4-8)

41

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) CACO3 CA(CH-01 CA(CH-02 CA(CH-03 HYDROGEN ACETONE BUTANONE PENTANON NONANONE ISOPROPANOL BUTANOL PENTANOL HEPTANOL NONANOL

KETS -14.6 7.80 0 0.619 25.2 62,893 15.5 0 0 0.0300 0 7.00 0.200 0.500 1.90 0 0 0 0 0

KT-CACO3 -15 0.0400 0 0.619 25.2 62,896 15.5 0 0 0.0300 0 7.00 0.200 0.500 1.90 0 0 0 0 0

OH 300 3.00 0.997 3x10-3 10.0 9,711 0 0 0 0.0300 0.0500 0 0 0 0 7.22 0.180 0.560 0.0200 1.91

SAL-DEH 163.1 6.00 0 1.00 25.2 62,572 1.30 19.2 1.40 3.30 0 0 0 0 0 0 0 0 0 0

SALT 430 5.50 0 1.00 25.2 61,989 1.30 19.2 1.40 3.30 0 0 0 0 0 0 0 0 0 0

SALTS 430 5.50 0 1.00 25.2 61,989 1.30 19.2 1.40 3.30 0 0 0 0 0 0 0 0 0 0

42

Table 4-9. Heat balances for Ketonization equipments Type Heater Heater Heater Cooler Cooler Pumps Pumps Compressor Reactor Reactor Unit H-107 H-108 H-109 C-102 C-103 P-105 P-106 CM-103 R-107 R-108 Heat duty [kJ/sec] 583 905 2,515 3,629 1,163 3.10 25.2 1,281 4,580 -2,615 Heat duty [kJ/h] 2.10x106 3.26x106 9.05x106 1.31x107 4.19x106 1.12x104 9.07x104 4.61x106 1.65x107 -9.41x106

Lime kiln (Unit 5)

In LIME KIL block the calcium carbonate labeled as CACO3 that come from KETONIZA block is divided in two streams: (i) the stream labeled as CACO3-2 with a flow of 9.20 ton/h is converted into quick lime (CaO). And (ii) the second stream labeled as CACO3-1 with a flow of 6.30 ton/h is recycled to a PRET-FER block for Fermentation process as was explained in that block before. The lime kiln simulation is shown in Figure 4-7. The conversion factor for Equation 4-5 in the reactor R-109 is 1, with an

endohothermic enthalpy of 4,529 kJ/ (Gosseaume, 2011). Table 4-11 shows the mass and heat balance of this process.

(Eq. 4-5)

43

Figure 4-7. Lime kiln simulation

Table 4-10. Heat balances for Lime kiln equipments Type Cooler Heater Reactor Unit C-104 H-110 R-109 Heat duty [kJ/sec] 521 987 4,529 Heat duty [kJ/h] 1.88x106 3.55x106 1.63x107

44

Table 4-11. Lime kiln mass and heat balance CACO3 CACO3-1 CACO3-2 CACO3-3 Temperature (C) 130 130 130 500 Pressure (bar_a) 7.60 7.60 7.60 1.00 Mass vapor fraction 0 0 0 0 Mass solid fraction 1.00 1.00 1.00 1.00 Mass flow (ton/h) 15.54 6.3 9.24 9.24 51,675 20,949 30,725 29,738 Enthalpy (kJ/s) Component mass flow (ton/h) CO2 0 0 0 0 CACO3 15.54 6.30 9.24 9.24 CAO 0 0 0 0 CAO 500 1.00 0.440 0.560 9.24 25,209 4.06 0 5.18 CAO-CO2 55.0 1.00 0.440 0.560 9.24 26,310 4.06 0 5.18

Final (Unit 6)

The final block includes the mixed alcohols (stream labeled as OH in Figure 4-8) conversion produce hydrocarbon fuels by alcohols dehydration olefins oligomerization (product stream labeled as OLF-C9-12 in Figure 4-8) and olefin hydrogenation (product stream labeled as PARAFIN in Figure 4-8). The final block simulation is shown in Figure 4-8. The alcohols dehydration from stream labeled OH to produced 7.30 ton/h of olefins C3 to C9 stream labeled as OLF-C3-9 in Figure 4-8, occurred in reactor R-110, where the conversion factor is 1 for the reactions shown in Appendix A (Eq. A-23 to A-28) (Gosseaume, 2011). The heat duty for an endothermic reaction is 1,892kJ/s (Table 4-13). The olefins produced in R-110 goes to a Oligomerization process to produced 7.30 ton/h of olefins C3 to C12 stream labeled as OLF-C3-12 in Figure 4-8, these reactions were present in reactor R-111. In Table A-2 (Appendix A) are shown the conversion factors for

45

reactions by the Equations A-29 to A-36.The heat duty for an exothermic reaction is 1,645kJ/s (Table 4-13). To improve fuel quality, the olefins labeled as OLEFIN in Figure 4-8 were hydrogenated to make 7.30 ton/h of corresponding paraffins (stream labeled as PARAFIN in Figure 4-8) in reactor R-112, where the conversion factor is 1 (Gosseaume, 2011). Olefin hydrogenation reactions are presented in Equations A-37 to A-45 (Appendix A). And the heat duty for an exothermic reaction is -2,421kJ/s (Table 4-13). In this block, the net demand of hydrogen is 0.0190 ton H2/ton hydrocarbon fuels; this hydrogen is produced in gasification block explained in the next section. Finally, the hydrocarbon fuel labeled as HC in Figure 4-8 is distilled into C8- and C9+ fractions. The light fraction and the heavy fraction can be used as blending components for gasoline and jet fuel, respectively, as Pham et al., (2012) mentioned. A ratio of 53 gallons of light fraction per ton of biomass is obtained for a total of 2,127 gallon/h of gasoline. And for heavy fraction the ratio is 19 gallons per ton of biomass for a total of 762 gallon/h of jet. Table 4-12 shows the material balance of the entire block. On the other hand, heat balances for this block shows a power consumption of 997 kW for compressor CM-104 and CM-105 (Table 4-13). The cooling demand in this block is 4,470kJ/s and the heating demand is 1,536kJ/s. Figure 4-9 shows a comparison between the gasoline obtained by MixAlco and a mixture of light naphtha (LVN) and gases fossil fuel consulted in an article of Cartagena refinery (Fernndez, 2007). The gasoline curve obtained by MixAlco had a similar behavior of LVN except for gas fraction.

46

Figure 4-8. Final simulation

Table 4-12. Final mass and heat balance C3 Temperature (C) 130 Pressure (bar_a) 55.0 Mass vapor fraction 0.770 Mass solid fraction 0.230 Mass flow (ton/h) 0.130 32.0 Enthalpy (kJ/s) Component mass flow (ton/h) H2 43 0.900 1.00 0 0.100 7.97 H2961 55.0 1.00 0 0.100 537 H2-1 130 55.0 1.00 0 0.100 537 H20 300 3.00 1.00 0 2.60 9.17 HC 130 55.0 0 0 7.40 4.04 HC-C4--8 HC-C9-12 HEAVY LIGHT 266 408 25 25 50.0 53.0 1.00 1.00 0 0 0 0 0 0 0 0 5.30 2.10 2.10 5.30 2,081 481 1,228 3,382

47

WATER CA(CH-03 HYDROGEN C3H6 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C11H24 C12H26

C3 0 0.0300 0 0.100 0 0 0 0 0 0 0 0 0

H2 0 0 0.100 0 0 0 0 0 0 0 0 0 0

H20 0 0.100 0 0 0 0 0 0 0 0 0 0

H2-1 0 0 0.100 0 0 0 0 0 0 0 0 0 0

H20 2.60 0 0 0 0 0 0 0 0 0 0 0 0

HC 0 0 0 0 0.0900 0.200 4.73 0.0300 0.230 1.41 0.0400 0.190 0.450

HC-C4--8 HC-C9-12 HEAVY LIGHT 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.0900 0 0 0.0900 0.20 0 0 0.200 4.73 0 0 4.73 0.0300 0 0 0.0300 0.230 0 0 0.230 0 1.41 1.41 0 0 0.0400 0.0400 0 0 0.190 0.190 0 0 0.450 0.450 0

(Continued Table 4-12) OH 300 3.00 0.997 3x10-3 10.0 9,711 OLEFIN 130 54.5 0.0390 4x10-3 7.40 1,699 0 0.030 OLF 399.9 55.0 0.996 4x10-3 7.40 287 0 0.030 OLF-C3-9 300 3.00 0.997 3x10-3 10.0 7,819 2.56 0.030 OLF-DEH 300 3.00 0.996 4x10-3 7.40 289 0 0.030 OLFC3-12 300 3.00 0.997 3x10-3 10.0 9,464 2.56 0.030 PARAFIN 130 55.0 7x10-3 4x10-3 7.50 4,073 0 0.030

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) WATER 0 CA(CH-03 0.030

48

HYDROGEN ISOPROPANOL BUTANOL HEXANOL PENTANOL HEPTANOL NONANOL C3H6 C4H8 C5H10 C6H12 C7H14 C9H18 C8H16 C10H20 C11H22 C12H24 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C11H24 C12H26

OH 0.050 7.22 0.180 0 0.560 0.0200 1.91 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

OLEFIN 0.050 0 0 0 0 0 0 0.100 0.0900 0.190 4.62 0.0300 1.38 0.230 0.0400 0.180 0.450 0 0 0 0 0 0 0 0 0

OLF 0.050 0 0 0 0 0 0 0.100 0.0900 0.190 4.62 0.0300 1.38 0.230 0.0400 0.180 0.450 0 0 0 0 0 0 0 0 0

OLF-C3-9 0.050 0 0 0 0 0 0 5.05 0.140 0.450 0.00 0.0100 1.67 0 0 0 0 0 0 0 0 0 0 0 0 0

OLF-DEH 0.050 0 0 0 0 0 0 0.100 0.0900 0.190 4.62 0.0300 1.38 0.230 0.0400 0.180 0.450 0 0 0 0 0 0 0 0 0

OLFC3-12 0.050 0 0 0 0 0 0 0.100 0.0900 0.190 4.62 0.0300 1.38 0.230 0.0400 0.180 0.450 0 0 0 0 0 0 0 0 0

PARAFIN 0.010 0 0 0 0 0 0 0.101 0 0 0 0 0 0 0 0 0 0.0900 0.200 4.73 0.0300 0.230 1.41 0.0400 0.190 0.450

49

Table 4-13. Heat balances for Final equipments Type Heater Cooler Cooler Cooler Cooler Cooler Compressor Compressor Reactor Reactor Reactor Unit Reboiler T-101 C-105 C-106 C-107 C-108 Condenser T-101 CM-104 CM-105 R-110 R-111 R-112 Heat duty [kJ/sec] 1,536 381 1,987 1,301 746 54.6 577 420 1,893 -1,645 -2,421 Heat duty [kJ/h] 5.53x106 1.37x106 7.15x106 4.68x106 2.69x106 1.97x105 2.08x106 1.51x106 6.81x106 -5.92x106 -8.72x106

Figure 4-91. Distillation curve for gasoline

Figure 4-10 shows a comparison between the jet obtained by MixAlco and jet fossil fuel consulted in an article of Cartagena refinery (Fernndez, 2007). The jet curve

50

obtained by MixAlco had a similar behavior of jet fossil fuel except for the final temperature, where the jet in MixAlco is lighter for about 56.0C.

Figure 4-10. Distillation curve for Jet

Gasification (Unit 7)

The last block in MixAlco process is GASIFICA shown in Figure 4-11. All hydrogen demand in MixAlco process is obtained in this block. In reactor R-113 is simulated the gasification of biomass undigested that come from pretreatment (stream labeled as BIOPRET in Figure 4-11) and fermentation (stream labeled as BIOM-FER in Figure 4-11) process and is converted to hydrogen (stream labeled as BM-C-H2O) for a production of 0.200 ton/h. The conversion factor for reactions Eq. 4-6 and 4-7 are 0.280 and 0.680, respectively (Gosseaume, 2011). Also, it is produced 3.20 ton/h of CO, 8.00 ton/h of CO2 and 3.10 ton/h of water. The vapor obtained in gasification is separated in S-107 to the char; where the obtained gas is called as SYNGAS. In order to use the heat duty of this gas a power generation is installed producing a work of 1,180 kW from the turbine TR-101.

51

Figure 4-11. Gasification simulation

After power generation, the syngas produce more hydrogen (0.250 ton/h) by the steam-gas shift reactor (R-114), the conversion factor for Equation 4-8 is 1 (Gosseaume, 2011). Table 4-14 shows the mass balance for this block. Table 4-15 show the heat balances for the equipment, where a power demand is 28.7 kW for pump P-107, the cooling demand is 5.07 kJ/s, and the exothermic duty is 10,555kJ/s for reactor R-113 and R-114. (Eq. 4-6) (Eq. 4-7) (Eq. 4-8)

52

Table 4-14. Gasification mass and heat balance BIO BIO-PRET BIOM BIOMAS BM-C-H2O C+H2+H20 CHAR 55.0 1.00 0 1.00 8.70 20,498 2.80 2.80 3.20 0 0 0 0 0 0 0 0 55.0 1.00 0.500 0.500 16.1 46,334 1 0.400 6.90 0 0 0 0 0 7.80 0 0 760 1.00 0.900 0.100 31.6 55,629 3.80 3.10 1.90 0 0 3.10 0 3.20 15.8 0.400 0.200 254 1.00 1.00 0 22.8 54,051 0 0 0 0 0 1.07 0 0 20.9 0.400 0.500 760 1.00 0 1.00 8.8 7,359 3.8 3.1 1.9 0 0 0 0 0 0 0 0 CO2 GAS H2 43.0 0.900 1.00 0 0.5 32.28 0 0 0 0 0 0 0 0 0 0 0.500 H2+ 43.0 0.900 1.00 0 22.8 55,749 0 0 0 0 0 1.10 0 0 20.9 0.400 0.500

Temperature (C) 55.0 55.0 Pressure (bar_a) 1.00 1.00 Mass vapor fraction 0.500 0 Mass solid fraction 0.500 0.0200 Mass flow (ton/h) 24.8 432 Enthalpy (kJ/s) 46,334 1,854,269 Component mass flow (ton/h) CELLU-01 3.80 2.80 XYLAN 3.10 2.80 LIGNI-01 10.1 3.20 SOLSL-01 0 5 SOLUN-01 0 0 WATER 0 418 AIR 0 0 CO 0 0 CO2 7.80 0 O2 0 0 HYDROGEN 0 0 (Continued Table 4-14) Temperature (C) Pressure (bar_a) Mass vapor fraction Mass solid fraction H2O+02 43.0 0.900 0.900 0 H20 95.0 63.0 0 0

43.0 254 0.900 0.800 1.00 1.00 0 0 20.9 22.8 51,803 52,791 0 0 0 0 0 0 0 0 20.9 0 0 0 0 0 0 0 3.10 0 3.20 15.8 0.400 0.200

LIQSAT 90.0 0.800 0 0

O2 25.0 1.00 1.00 0

O2+H20 STEAMSAT STEAMSUP SYNGAS 43.0 162 577 760 0.900 1.00 62.0 1.00 0.300 1.00 1.00 1.00 0 0 0 0

WAT 55.0 1.00 0 0

WATER 95.0 63.0 0 0

53

H2O+02 H20 LIQSAT O2 O2+H20 STEAMSAT STEAMSUP SYNGAS WAT WATER Mass flow (ton/h) 1.90 5.00 5.00 10.0 1.40 5.00 5.00 22.8 417 5.00 -13 6 Enthalpy (kJ/s) 4,067 21,624 21,655 3,2x10 4,662 18,283 17,102 4,067 1.83x10 21,626 Component mass flow (ton/h) CELLU-01 0 0 0 0 0 0 0 0 0 0 XYLAN 0 0 0 0 0 0 0 0 0 0 LIGNI-01 0 0 0 0 0 0 0 0 0 0 SOLSL-01 0 0 0 0 0 0 0 0 5 0 SOLUN-01 0 0 0 0 0 0 0 0 0 0 WATER 1.07 5.00 5.00 0 1.07 5.00 5.00 3.14 412 5.00 AIR 0 0 0 0 0 0 0 0 0 0 CO 0 0 0 0 0 0 0 3.20 0 0 CO2 0 0 0 0 0 0 0 15.8 0 0 O2 0.370 0 0 10.0 0.380 0 0 0.370 0 0 HYDROGEN 0.500 0 0 0 0 0 0 0.220 0 0 Table 4-15. Heat balances for Gasification equipments Type Cooler Cooler Heat exchanger Pumps Turbine Reactor Reactor Unit C-109 C-110 E-112 P-107 TR-101 R-113 R-114 Heat duty [kJ/sec] 1,698 3,372 4,522 28.7 -1,181 -9,295 -1,260 Heat duty [kJ/h] 6.11x106 1.21x107 1.63x107 1.03x105 -4.25x106 -3.35x107 -4.54x106

54

4.1.1.2

MixAlco overall mass balance results

In numeral 3.1.1.1 was described mass and heat balances for MixAlco process. Table 4-16 summarized some relations discussed in that numeral. The theoretical relations helps to verified that results obtained in the simulation are according to the literature review. The sources consulting for these relations are: (Pham et al., 2010), (Sierra et al., 2010), (Holtzapple, 2004), (Gosseaume, 2011). Table 4-16. MixAlco yields
Unit Parameter Biomass feed (ton/h) CaO feed Total (ton/h) CaO feed recycle (ton/h) CaO feed make up (ton/h) H2O to Feed-Handling (ton/h) Ca(OH)2 Production (ton/h) Cellulose digested (ton/h) Xylan digested (ton/h) Lingni digested (ton/h) Volatile solid = biomass VS (ton/h) Conversion Biomass digested (ton/h) Biomass undigested (ton/h) Air consumption (ton/h) H2O to pretreatment (ton/h) Value 40.0 6.07 5.17 0.900 2.00 7.90 14.3 4.90 7.00 34.3 26.2 8.10 6.70 400 Calculated relations 0.150 Total ton CaO/ton Biomass 0.127 ton CaO recycle /ton Biomass 0.0225 ton CaO Make up /ton Biomass 0.0500 ton H2O Make up /ton Biomass 0.200 ton Ca(CHO)2 /ton Biomass 85.0% of Cellulose inlet 65.0% of xylan inlet 70.0% of lingni inlet 0.800 ton biomass VS / ton Biomass 0.800 ton digested / ton biomass VS 0.200 ton undigested / ton biomass VS 0.170 ton Air /ton Biomass 10.0 ton H2O /ton Biomass Theoretical relations 0.150 Total g CaO/g Biomass 0.0230 g CaO Make up /g Biomass

Feed Handling

85.0% of Cellulose inlet 65.0% of xylan inlet 70.0% of lingni inlet 0.800 g digested / g volatile solid fed 0.200 ton undigested / ton biomass VS 5.00 to 15.00 ton H2O /ton Biomass (6 / 42) 0.600 ton carboxylate salts / ton Biomass

Pretreatment

Reaction time (week / days) Fermentation Carboxylate salts (ton/h)

(6/42) 24.0 0.60ton carboxylate salts / ton Biomass

55

Unit

Parameter Volatile fatty acid (VFA) (ton/h) Selectivy Mixed acid yield H2O to fermentation (ton/h) CaCO3 total (ton/h) CO2 produced (ton/h) Reaction time (week / days) CaCO3 production (ton/h) Ketones (ton/h) Alcohols (ton /h)

Value Calculated relations 19.0 1.26 ton salt / ton VFA 0.700 0.600 200 14.3 7.80 (8/56) 14.2 9.60 9.87 0.287 9.20 6.30 5.20 7.30 2.56 7.37 0.140 ton VFA / ton digested ton VFA / ton biomass VS 5.00 ton H2O /ton Biomass 0.400 Total ton CaCO3 /ton Biomass 0.200 ton CO2 /ton Biomass 0.360 ton CaCO3 /ton Biomass 0.510 ton ketones/ ton VFA 0.520 ton alcohol / ton VFA 0.250 ton alcohol / ton Biomass 0.0290 ton H2 demand / ton alcohol 0.00700 ton H2 demand / ton Biomass

Theoretical relations 0.650 g carboxylic acids / g volatile solids digested 0.520 ton VFA / ton biomass VS 5.00 ton H2O /ton Biomass 0.400 Total ton CaCO3 /ton Biomass 0.200 ton CO2 /ton Biomass (8 / 56) 0.360 ton CaCO3 /ton Biomass 0.510 g ketones/ g carboxylic acids 0.520 ton alcohol / ton VFA 0.250 ton alcohol / ton Biomass 0.0225 kg H2 / kg mixed alcohol 0.00687 kg H2 demand / kg Biomass

Ketonization

Ketone Hydrogenatio H2 consumption (ton /h) n CaCO3 to lime kiln (ton/h) CaCO3 to fermentation (ton/h) CaO for recycle to feed handling (ton/h) Olefins (ton/h) H2O produced (ton/h) Parafins (ton/h) H2 consumption (ton /h)

Lime kiln

Alcohol Dehydration Olefin hydrogenatio n

0.180 ton Olefin / ton Biomass 0.350 ton H2O produced / ton Olefin 0.0190 ton H2 demand / ton Parafin 0.00350 ton H2 demand / ton Biomass 0.400 g Light hydrocarbon yield /g alcohol 0.200 g Heavy hydrocarbon yield /g alcohol 53 gallons Light hydrocarbon /ton Biomass 0.0139 kg H2 / kg hydrocarbon fuels 0.00340 kg H2 demand / kg Biomass 0.600 g Light hydrocarbon yield /g alcohol 0.200 g Heavy hydrocarbon yield /g alcohol 62.0 gallons Light hydrocarbon /ton Biomass

Light hydrocarbon (C8-) (ton/h) Final Heavy hydrocarbon (C9+) (ton/h) Light hydrocarbon (gallon/h)

5.28 2.09 2127

56

Unit

Parameter Heavy hydrocarbon (gallon/h) H2 produced in gasification (ton/h) H2 produced in Steam-gas shift (ton/h)

Value 762 0.200 0.250

Calculated relations 19 gallons Heavy hydrocarbon /ton Biomass

Theoretical relations 19.0 gallons Heavy hydrocarbon /ton Biomass

Gasification & Steam-gas shift

4.1.1.3

MixAlco overall heat balance results

Table 4-17 shows a summary of heat balances for the equipment simulated in MixAlco process, where the total heating demand is 120,288 kJ/s (4.33x108 kJ/h). Also, the total cooling demand is 22,809 kJ/s (8.21x107 kJ/h); The total power required for pumps and compressors, without the power generated in the turbine TR-101 by the gasification process is 2,408 kJ/s (8.67x106 kJ/h). Table 4-17. Summary fo heat balances for MixAlco processs
HEATERS Feed handling (kJ/s) Pretreatment & Fermentation (kJ/s) Dewatering (kJ/s) Ketonization & Lime kiln (kJ/s) Final (kJ/s) Gasification (kJ/s) Total heat duty (kJ/s) Total heat duty (kJ/h) COOLERS PUMPS COMPRESSORS REACTORS -1,541 18,427 143,451 6,494 -2,174 -10,555 10,651 3.83x107 HEAT EXCHANGERS

7,957 113,762 4,990 1,536 120,288 4.33x108 5,313 4,470 5,070 22,809 8.21x107

30.0 28.0 28.0 87.0 3.11x105

10 1,215 1,281 997 -1,181 2,323 8.36x106

4,522 147,973 5.33x108

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Actual heat integration has a heat exchangers duty of 147,973 kJ/s (5.33x108kJ/h). signal stands for exothermic reactions, meanwhile positive stands for endothermic reactions. 4.1.2 Simulation build up and results for CODP base case

In Table 4-17, heat duty with negative

The CODP simulation was divided in four blocks to build up a simulation: two preheating trains, one atmospheric distillation unit and one vacuum distillation unit. The blocks are shown in Figure 4-12.

Figure 4-12. Blocks of CODP simulation

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4.1.2.1 CODP Block description First preheating train

Figure 4-13. First pre-heating train

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The crude oil (named CRUDE-IN) was feed to the first preheating train at 30.6C and 2.4bar_a. Figure 4-13 shows this process. This train was heat integrated with side stream OVHT204 from the atmospheric distillation, and with the second preheating train by the stream DIE203. The target was to heat the crude oil at 183.5C before enter to the second preheating train. This stream (fed stream of the second preheating train) was named CRDTP1. Table 4-18 shows the mass balance obtained for this process. On the other hand, Table 4-19 shows the heat balances for this block, where exist a cooling demand of 1.59x107 kJ/s for the cooler (C-201) plus the flash separator (SP-201); in this block did not exist heaters. The power required for pumps are 0.21MW.

Table 4-18. First train preheating mass and heat balance

CRD-IN CRDE201 CRDE203 CRDTP1 CRUDE-IN DIE203 Temperature (C) 31.8 127 183 183 30.6 236 Pressure (bar_a) 26.9 26.9 25.8 27.1 2.40 9.00 Mass vapor fraction 0 0 0 0 0 0 Mass flow (ton/h) 162 162 162 162 162 88.0 Enthalpy (kJ/s) 83,851 75,245 69,430 69,430 84,083 32,447 Component mass flow (ton/h) WATER 0 0 0 0 0 0 ETHANE 0 0 0 0 0 0 PROPANE 0.100 0.100 0.100 0.100 0.100 0 ISOBUTANE 0.100 0.100 0.100 0.100 0.100 0 N-BUTANE 0.200 0.200 0.200 0.200 0.200 0 ISOPENTANE 0.400 0.400 0.400 0.400 0.400 0 N-PENTANE 0.400 0.400 0.400 0.400 0.400 0 N-HEXANE 0.400 0.400 0.400 0.400 0.400 0 PSEUDOCOMPONENTS 160.4 160.4 160.4 160.4 160.4 87.7

60

(Continued Table 4-18)

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) WATER PROPANE ISOBUTANE N-BUTANE ISOPENTANE N-PENTANE N-HEXANE PSEUDOCOMPONENTS DIEST204 137.8 9.60 0 88.0 15,351 0 0 0 0 0 0 0 87.7 DIEST204 137.8 9.60 0 88.0 38,378 0 0 0 0 0 0 0 87.7 GAST204 0 1.70 0 0 0 0 0 0 0 0 0 0 0 MPAT204 137.8 9.60 0 52.8 23,027 0 0 0 0 0 0 0 52.5 OVH201 99.8 2.00 0.088 64.8 46,635 3.90 0.100 0.100 0.300 0.500 0.600 1.00 58.2

Table 4-19. Heat balances for equipments in 1st preheating train

Type Cooler Heat exchanger Heat exchanger Flash separator Pump Pump Unit C-201 E-201 E-203 SP-201 P-201 P-202 Heat duty [kJ/sec] 3,056 8,595 5,909 1,352 200 10 Heat duty [kJ/h] 1.10x107 3.09x107 2.13x107 4.87x106 7.20x105 3.60x104 Exchanger area [m2] NA 271 261

Second preheating train

The second preheating train was fed with the stream CRDTP1, which was at 183.5C and 27.1 bar_a. Figure 4-14 shows, this process. As the first preheating train, this train was heat integrated with side stream DIEST-04 from the atmospheric distillation, and with side streams ASPAHLT and HVGO-205 from the vacuum distillation The target was to take the CRDTP1 stream conditions to 277.2C (atmospheric tower conditions).

61

The resulting stream from this train was named CRDT204. Table 4-20 shows the mass balance of this process. On the other hand, Table 4-21 shows the energy balances for this block, where exist a cooling demand of 9.25x106 kJ/s for the cooler (C-202); in this block did not exist heaters.

Figure 4-14. Second pre-heating train

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Table 4-20. Second train preheating mass and heat balance

ASFP205 ASPHALT CRDE204 CRDE205 CRDE207 CRDTP1R Temperature (C) 389.9 285 215.8 246 277 183.5 Pressure (bar_a) 19.4 18.8 27.1 27 27 27.1 Mass vapor fraction 0 0 0 0 0 0 Mass flow (ton/h) 46.6 46.6 162 162 162 162 Enthalpy (kJ/s) 14,072 17,794 65,825 62,336 58,498 69,430 Component mass flow (ton/h) WATER 0 0 0 0 0 0 PROPANE 0 0 0.100 0.100 0.100 0.100 ISOBUTANE 0 0 0.100 0.100 0.100 0.100 N-BUTANE 0 0 0.200 0.200 0.200 0.200 ISOPENTANE 0 0 0.400 0.400 0.400 0.400 N-PENTANE 0 0 0.400 0.400 0.400 0.400 N-HEXANE 0 0 0.400 0.400 0.400 0.400 PSEUDOCOMPONENTS 46.6 46.6 160.4 160.4 160.4 160.4

(Continued Table 4-20)

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) WATER PSEUDOCOMPONENTS DIEST204 288.8 13.1 0 88.0 28,958 0 87.7 DISE205 236.1 9.00 0 88.0 32,447 0 87.7 GPVE204 189.5 12.8 0 36.9 16,049 0 36.9 GPVT205 74.5 12.8 0 36.9 18,608 0 36.9 HVGO 323.7 12.9 0 36.9 12,444 0 36.9

Table 4-21. Heat balances for equipments in 2nd preheating train

Type Cooler Heat exchanger Heat exchanger Heat exchanger Unit C-202 E-204 E-205 E-207 Heat duty [kJ/sec] 2,570 3,596 3,477 3,753 Heat duty [kJ/h] 9.25x106 1.29x107 1.25x107 1.35x107 Exchanger area [m2] NA 439 439 220

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Atmospheric distillation unit

The atmospheric distillation unit is shown in Figure 4-15. The atmospheric distillation column (named T-204) is considered the master unit, because different cuts of the oil crude were obtained. This column had one stripper, two pumparounds, furnace and condenser. The components of the feed stream were separated as: gas, naphtha, jet, diesel, gas oils and atmospheric residues.

Figure 4-15. Atmospheric distillation column

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Due to the large amount of heat duty from gas and diesel product streams, those were heating integrated with the first and second preheating trains. Table 4-22 shows the mass balance. The crude oil named (CRDPREC) fed this tower, which was at 277.2C and 27.1 bar_a. The yields obtained in this unit are shown in numeral 5.1.2.2 Table 4-23 shows the energy balances for this block, where exist a cooling demand of 6.86x107 kJ/s for the cooler (C-203), the condenser, the pumparounds and the separators; the total heating demand is 9.64x107 kJ/s for the heater (H-201) and the furnace. The power demands for pumps are 0.0230 MW. Table 4-22. Atmospheric distillation mass and heat balance
AGOP204 AGOT204 CRDH202 CRDPREC DIEM201 DIEST204 GAS-S203 GAST4 JET-T204 JETP203 Temperature (C) 358.3 357 226.9 277.2 288.8 304 98.3 97.8 69.5 194.4 Pressure (bar_a) 12.9 2.20 19.1 27.0 13.1 2.20 1.70 1.70 13.9 13.9 Mass vapor fraction 0 0 0 0 0 0 1.00 1.00 0 0 Mass flow (ton/h) 6.40 6.40 162 162 88.0 35.0 0 11.2 19.8 19.8 Enthalpy (kJ/s) 1,861 1,977 64,545 58,498 28,958 11,397 0 11,979 9,304 7,676 Component mass flow (ton/h) WATER 0 0 0 0 0 0 0 2.10 0 0 PROPANE 0 0 0.100 0.100 0 0 0 0.100 0 0 ISOBUTANE 0 0 0.100 0.100 0 0 0 0.100 0 0 N-BUTANE 0 0 0.200 0.200 0 0 0 0.200 0 0 ISOPENTANE 0 0 0.400 0.400 0 0 0 0.400 0 0 N-PENTANE 0 0 0.400 0.400 0 0 0 0.300 0 0 N-HEXANE 0 0 0.400 0.400 0 0 0 0.400 0 0 PSEUDOCOMPONENTS 6.20 6.20 160.4 160.4 87.7 35.0 0 7.70 19.8 19.8

65

(Continued Table 4-22)

JETT204 LIGNAPH MPAM201 MPAT204 NAPHT204 OVHT204 RESIDUE STEAM-4 STEAM-JT WATSP203 Temperature (C) 193.5 98.3 278.9 147.7 97.8 144.4 365.6 352.8 353.3 98.3 Pressure (bar_a) 2.90 1.70 2.20 2.20 1.70 2.20 2.20 5.10 5.10 1.70 Mass vapor fraction 0 0 0 0 0 1.00 0 1.00 1.00 0 Mass flow (ton/h) 19.8 2.60 52.9 52.9 4.40 64.8 88.7 3.20 0.600 1.60 Enthalpy (kJ/s) 7,676 1,396 17,561 22,562 8,373 38,029 27,563 11,281 2,093 6,978 Component mass flow (ton/h) WATER 0 0 0 0 1.60 3.90 0 3.20 0.600 1.60 PROPANE 0 0 0 0 0 0.10 0 0 0 0 ISOBUTANE 0 0 0 0 0 0.10 0 0 0 0 N-BUTANE 0 0 0 0 0 0.30 0 0 0 0 ISOPENTANE 0 0 0 0 0 0.50 0 0 0 0 N-PENTANE 0 0 0 0 0 0.60 0 0 0 0 N-HEXANE 0 0 0 0 0 1.00 0 0 0 0 PSEUDOCOMPONENTS 19.8 2.60 52.9 52.9 2.70 58.2 88.7 0 0 0

Table 4-23. Heat balances for equipment in atmospheric distillation unit

Type Heater Heater Cooler Cooler Cooler Cooler Flash separator Flash separator Pump Pump Unit H-201 Furnace C-203 Condenser Pumparound MPA Pumparound MPACAL SP-202 SP-203 P-203 P-204 Heat duty [kJ/sec] 4,922 21,848 1,614 5,774 5,113 563 5,972 10.0 16.0 7.00 Heat duty [kJ/h] 1.77x107 7.87x107 5.81x106 2.08x107 1.84x107 2.03x106 2.15x107 3.60x104 5.76x104 2.52x104

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Vacuum distillation unit The vacuum distillation unit is shown in Figure 4-16. In the vacuum distillation column (named T-205), the crude oil was fed

with the bottom stream of T-204. In order to prevent the breakdown of the reduced crude, this unit worked at high temperatures and vacuum pressure. The obtained cuts were: gas, light gas oil, heavy gas oil, and vacuum residue. Due to the large amount of heat duty from HVGOT205 and ASPHALT product streams, those were heating integrated with the second preheating train.

Figure 4-16. Vacuum distillation column

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Table 4-24 shows the mass balance obtained for this unit. The crude oil named (CRDT204) fed this tower, which was at 365.6C and 2.2 bar_a. The yields obtained in this unit are shown in numeral 5.1.2.2. Table 4-25 shows the energy balances for this block, where exist a cooling demand of 3.99x107 kJ/s for the cooler (C-204), the condenser, the pumparounds and the separators; the total heating demand is 2.44x107 kJ/s for the heater (H-202). The power demand for the pump P-205 is 0.0480 MW. Table 4-24. Vacuum distillation mass and heat balance
Temperature (C) Pressure (bar_a) Mass vapor fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) PSEUDOCOMPONENTS AGO 48.9 1.20 0 0 0 0 ASPHALT 388.7 0.100 0 46.6 14,072 46.6 ASPHP205 389.9 19.4 0 46.6 14,072 46.6 CRDH202 365.6 1.00 0 88.8 27,563 88.7 CRDT204 365.6 2.20 0 88.8 27,563 88.7 CREDT205 432.2 0.100 0.590 88.8 20,817 88.7 GAS-S204 1.20 0 0 0

Temperature (C) Pressure (bar_a) Mass vapor fraction Mass flow (ton/h) Enthalpy (kJ/s) Component mass flow (ton/h) WATER PSEUDOCOMPONENTS

GPVM7 323.7 12.9 0 36.9 12,444 0 36.9

HVGOT205 323.8 0.100 0 36.9 12,444 0 36.9

LVGO-205 34.5 10.2 0 5.30 2,675 0 5.30

LVGOT205 213.4 0.100 0 5.30 2,210 0 5.30

OVHT205 60 0 1.00 3.00 11,165 3.00 0

STEAM-5 454.4 3.70 1.00 3.00 10,467 3.00 0

WAT-S204 48.9 1.20 0 3.00 13,142 3.00 0

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Table 4-25. Heat balances for equipments in vacuum distillation unit Type Heater Cooler Cooler Cooler Cooler Cooler Flash separator Pump Unit H-202 C-204 Condenser Pumparound UPA Pumparound MPA Pumparound MPACAL SP-204 P-205 Heat duty [kJ/sec] 6,780 567 308 2,117 5,874 219 2,011 48.0 Heat duty [kJ/h] 2.44x107 2.04x106 1.11x106 7.62x106 2.11x107 7.88x105 7.24x106 1.73x105

4.1.2.2

CODP Overall mass balances results Table 4-26 shows the yields for CODP. Defined yield as the mass ration between

refined products and the initial crude oil feed. A column pseudo-stream was used for internal column calculations, but this pseudo-stream was not included in the column material balance.

Table 4-26. COPD Yields

Process Atmospheric column Parameter Yield (ton Naphta from T-204 /ton crude) Yield (ton Jet from T-204 /ton crude) Yield (ton Diesel from T-204 /ton crude) Yield (ton AGO from T-204 /ton crude) Vacuum column Yield (ton LVGO from T-205 /ton crude) Yield (ton HVGO from T-205 /ton crude) Yield (ton VGO from T-205 /ton crude) Yield (ton Asphalt from T-205 /ton crude) 0.033 0.228 0 0.287 Value 0.017 0.123 0.217 0.04

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4.1.2.3 CODP Overall heat balances results Table 4-27 shows a summary of heat balances for equipments in CODP, the C for separators means the needed heat is for cooling and the H is for heating. So, the total heating utility is calculated as the duty for heaters plus the heat needed in separators with a total duty of 1.26x108 kJ/s. Likewise, the total cooling utility is calculated with the coolers duties plus the cooling duty needed in separators with a total duty of 1.29x108 kJ/s. Table 4-27 also shows the heat exchangers used in CODP for the first and second preheating trains. And the power required for pumps with a total power demand of 0.280 MW. Table 4-273. Overall heat balances for CODP
HEATERS COOLERS PUMPS SEPARATORS HEAT EXCHANGERS 14,504 3,056 210 1,352 (C) 2,570 26,770 6,780 33,550 1.21x108 13,064 9,085 27,775 1.00x108 23.0 48.0 281 1.01x106 5,982 (H) 2,011 (H) 9,345 3.36x107 25,330 9.12x107 10,826

1-Train (kJ/s) 2-Train (kJ/s) Atmospheric-unit (kJ/s) Vacuum-unit (kJ/s) Total heat duty (kJ/s) Total heat duty (kJ/h)

4.2 Define needs In this work, the need was defined as the technical-economical evaluation for a new MixAlco plant by retrofitting analysis with CODP, comparing with a base case (only a new MixAlco plant).

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4.3 Retrofitting procedure applied: Process arrangements 4.3.1 Internal rearrangements The first loop of the proposed methodology covers only internal arrangements. With the aim of apply this first step, an improvement within each plant (MixAlco and CODP) with a mass and energy integration was proposed. This integration did not require any addition of new equipment in each plant, according to the methodology. 4.3.1.1 MixAlco process - Mass integration Appendix C shows a literature review of mass integration. In the base case, MixAlco process was using a mass integration of calcium carbonate between ketonization, pretreatment, and fermentation units. In this integration, the byproduct stream of calcium carbonate from ketonization is sent to fermentation unit as buffer salt. The remaining amount is treated in a lime kiln to produce quick lime, needed in the pretreatment process. Regardless, it is necessary use a make up of these substances. (Gosseaume, 2011). Tables 4-28 and 4-29 show the mass balances obtained for fresh and waste streams in the simulation.

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Table 4-28. Fresh MixAlco streams

Process Stream Name Temperature (C) Pressure (bar_a) Mass Vapor Fraction Mass Solid Fraction Total mass flow (ton/h) Component mass flow (ton/h) CELLU-01 XYLAN LIGNI-01 SOLSL-01 WATER CAO CACO3 NITROGEN O2 FEED HANDLING PRETREATMENT FERMENTATION GASIFICATION H2O-LIME CAO-MAKE BIOMASS H20-PRET AIR H20-FERM MK-CACO3 O2 WATER 25.0 55.0 25.0 25.0 25.0 50.0 25.0 25.0 95.0 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 63.0 0 0 0 0 1.00 0 0 1.00 0 0 1.00 0.870 0 0 0 1.00 0 0 2.00 0.900 39.5 400 6.70 200 9.30 10.0 5.00 0 0 0 0 2.00 0 0 0 0 0 0 0 0 0 0.900 0 0 0 16.8 7.50 10.0 5.17 0 0 0 0 0 0 0 0 400 0 0 0 0 0 0 0 0 0 0 0 5.30 1.40 0 0 0 0 200 0 0 0 0 0 0 0 0 0 0 9.30 0 0 0 0 0 0 0 0 0 0 10.0 0 0 0 0 5.00 0 0 0 0

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Table 4-29. Waste MixAlco streams

Process Stream Name Temperature (C) Pressure (bar_a) Mass Vapor Fraction Mass Solid Fraction Total mass flow (ton/h) Component mass flow (ton/h) CELLU-01 XYLAN LIGNI-01 SOLSL-01 WATER CO2 CA(CH-03) O2 C3H6 DEWATERING WATDISTI 60.0 5.50 0 0 200 0 0 0 0 200 0 0 0 0 FINAL H2O 300 3.00 1.00 0 2.60 0 0 0 0 2.60 0 0 0 0 C3 130 55.0 0.770 0.230 0.132 0 0 0 0 0 0 3.2x10-2 0 0.100 WAT 55.0 1.00 0 0 407 0 0 0 5.00 402 0 0 0 0 GASIFICA O2+H20 CHAR 43.0 760 0.900 1.00 0.300 0 0 1.00 1.45 8.76 0 0 0 0 1.07 0 0 0.380 0 3.77 3.11 1.88 0 0 0 0 0 0

CO2 43.0 0.900 1.00 0 20.9 0 0 0 0 0 20.9 0 0 0

The author of this work perceived the possibility to make a mass integration using the resulting impurity-free water from the dewatering and gasification process stream (WAT DISTI) in block DEWATER and stream (WAT) in block GASIFICA as explained in Section 4.1.1.1. This is proposed considering that fermentation and pretreatment processes do not need any special quality water; therefore, this stream gives an opportunity to supply a fraction of water needed for both processes.

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The integration was made using a simple recycle from dewatering and gasification units to fermentation and pretreatment units. Figure 4-17 shows this integration, where blue lines are fresh and waste water streams, black lines indicated intermediate streams and red lines show the recycle stream.

Figure 4-17. Mass integration for MixAlco process - Heat integration The base case for MixAlco process had energetic requirements for heating of 433GJ/h, and for cooling of 82.1 GJ/h. With the equipments considered, it is not possible to make low cost energy integration. However, power integration was made between the turbine (TR-101) in gasification and the power required by compressor (CM-103) in ketonization this is illustrated in Figure 4-18. After this integration, the power balances required for compressor are 2,323kJ/s (8.36 GJ/h).

Figure 4-182. Power integration for MixAlco process

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Furthermore, an energetic integration between endothermic and exothermic reactors for the entire process was made. This involves equipment all the MixAlco blocks, the energy flows rerouted is illustrated in Figure 4-19. Where black lines are heat or work fresh streams, and red lines show the recycle heat stream from exothermic reactors to endothermic reactors. After this integration, the general heat balances required in endothermic reactors are 10,651kJ/s (38 GJ/h).

Figure 4-19. Heat integration in Reactors for MixAlco process

Cost analysis Using all above integrations, the total Variable Operating Cost (VOC) for

MixAlco process was 36,493,756 USD per year. Table 4-30 shows the VOC for this process in detail. The highest cost was the Biomass that represents 42% of total VOC, following to utilities that represent 40% of total VOC, while the chemicals represent 13% of total VOC.

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Table 4-30. VOC of MixAlco process in base case

Rate Feedstock Sugarcane baggase Manure Chemical Lime Flocculant Iodoform CaCO3 Utility Fired Heat MP Steam Cooling Water LP Steam Refrigerant Electricity Material disposal Total VOC 32.0 ton/h 8.00 ton/h 0.900 10.0 3.20 9.00 33.7 208.438 3,298.46 0 2,721.87 13.0 6.00 ton/h kg/h kg/h ton/h ton/h ton/h m3/h ton/h m3/h MW ton/h Prices 60.0 USD/ton 10.0 USD/ton 70.0 USD/ton 991 USD/ton 25.0 USD/kg 50.0 USD/ton 2.50 USD/ton 4.40 USD/ton 0.00400 USD/m3 4.2 0USD/ton 0.0131 USD/ m3 0.0620 USD/kWh 18.0 USD/ton Annual cost (USD) 15,360,000 640,000 504,000 79,280 640,000 3,600,000 687,878 7,267,323 117,020 0 286,256 6,448,000 864,000 36,493,756

The Fixed Operating Cost (FOC) includes labor, maintenance and overhead operating costs. The number of total operators was calculated for eight process zones. Two zones were established to need two operators, and the resting six zones were established to need one operator. This resulted in a total of ten operators per shift; and the total shifts are five due to illness, vacations, holidays, training, and overtime during startups. The labor, maintenance and overhead operating cost accounts were based on (Seider, Seader, & Lewin, 2004) and (Peters, Timmerhaus, & West, 2004). The plant operating hours were established as 8000 per year. Besides, the lifetime for this project was 20 years. The depreciation method was 200% DDB for 9 years. The construction period was estimated in 1.5 years. And, the Startup period is 6 months.

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The FOC for MixAlco process was USD 15,596,880. Table 4-31 shows the FOC for this process in detail. The Maintenance was the highest cost represented in 58% of total FOC, following to labor that represents 29% of total FOC, while operating overhead represent 12.4% of total FOC. Table 4-31. FOC of MixAlco process in base case Labor Direct wage and benefits (DW&B) Direct salary and benefits Operating supplies and services Technical asistants to manufacturing control laboratory Maintenance Wages and benefits (MW&B) Salaries and benefits Materials and services Maintenance overhead Operating overhead General plant overhead Mechanical department services Employee relations department Business services Total FOC Annual cost (USD) 3,120,000 468,000 187,200 520,000 285,000 3,945,306 986,327 3,945,306 197,265 604,894 204,471 502,658 630,453 15,596,880

The Fixed Capital Investment (FCI) for MixAlco process is shown in Table 4-32, with a total of USD 112,723,032. Where, dewatering was the highest cost with 19.3%, most of dewatering cost comes from the crystallization equipment, following by gasification and Cogeneration with 12.9%, which represent that producing hydrogen from fermentation residues is expensive. The low-cost pile design, pretreatment and fermentation require the least investment, with 12.3% of total FCI approximated as Pham et al., (2010) study. Although,

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the long residence time of pretreatment and fermentation requires large piles, which have a volume of 160,000 m3 each (Pham et al., 2010). An installed cost of fermentator is calculated, scaling to 40 ton/h, based on previous study made by Holtzapple, (2004). Table 4-32. FCI for MixAlco process in the base case Pretreatment & Fermentation Dewatering Ketonization Ketone Hydrogenation Gasification & Cogeneration Steam Gas Shift & PSA* Dehydratation & Oligomerization Olefin Hydrogenation WWT** - Storage - Utility Total FCI % FCI 12.7 19.3 6.69 11.7 12.9 7.90 9.12 12.2 7.44 100 FCI (USD) 14,310,330 21,778,057 7,543,494 13,215,510 14,491,711 8,913,659 10,276,671 13,809,600 8,384,000 112,723,032

The Working Capital Investment (WCI) was calculated as 10% of FCI, with a total of USD 11,272,303. The Total Capital Investment (TCI) was calculated as WCI plus FCI, resulting in USD 123,995,335. Table 4-33 shows the obtained profitability results for MixAlco process with and without the time value of money.

Table 4-33. Summary MixAlco economic results in base case Parameter Profitability without the time value of money ROI estimated (%) Annual gross (pre tax) profit (USD) Annual net (after tax) profit (USD) PBP (years) 14.7 20,786,937 16,616,185 4.40 Value

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Parameter Total operating cost (USD) FCI (USD) WCI (USD) TCI (USD) Profitability with the time value of money NPV (USD) ROI real (%) Annual sales (USD) Tax rate (%) Discount rate (%)

Value 52,090,637 112,723,032 11,272,303 123,995,335

7,296,447 11.13 72,877,573 35 10%

The base case for MixAlco process results in a ROI of 11.129% that is not the desirable 15%, but is acceptable in current market conditions. However, the NPV represent a profitable project in USD 7,296,447. In sensibility analysis the variation of biomass, gasoline and jet prices showed an improvement in the obtained ROI. Currently, the prices for those products are: biomass (60.0 USD/gal), gasoline (3.38 USD/gal), and Jet (2.88 USD/gal). Furthermore, the results reported by Pham et al., (2010) shown a ROI

evaluation project of 10.0%. The PBP is about 4.40 years after start of operation. The cumulative discounted cash flow for this case is shown in the Figure 4-20. This shown that after paying all the expenses of the project, the revenues of the project will give net value of MM USD 7.30 in the present dollars.

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Figure 4-203. Cash flow for MixAlco process in the base case

4.3.1.2 CODP Integration of CODP separated from MixAlco was not an objective of this work, because this plant (as opposed to the MixAlco plant) is already built and operating. Nevertheless, in order to quantify economic benefits from possible integration rearrangements and for study completeness, the integration possibilities were also considered.

- Mass integration For CODP, it was not possible to make a low cost mass integration due to two reasons:

There are not waste streams at required temperature condition for this process; this results in additional heating equipment requirements. (Table 4-35)

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The waste water in CODP (Table 4-35) results in two streams. One of the streams contains impurities (petroleum fractions) and the other stream is impurity-free water. The water waste reuse is possible if new separation and heating equipment are introduced in order to use all the waste water.

Table 4-34 and 4-35 show mass balances obtained for fresh and waste streams in the simulation. Table 4-344. Fresh CODP streams
FIRST PREHEATING TRAIN Temperature(C) Pressure (bar_a) Mass Vapor Fraction Mass Liquid Fraction Total mass flow (ton/h) Component mass flow (ton/h) Water Ethane Propane Isobutane N-Butane Isopentane N-Pentane N-Hexane Pseudocomponents CRUDE-IN 30.0 2.40 0 1.00 162 0 0 5.48 x10-2 8.23 x10-2 2.21 x10-2 3.71 x10-2 3.58 x10-2 4.32 x10-2 160.5 ATMOSPHERIC UNIT STEAM-4 353 5.00 1.00 0 3.17 3.17 0 0 0 0 0 0 0 0 STEAM-JT 353 5.00 1.00 0 0.600 0.600 0 0 0 0 0 0 0 0 VACUUM UNIT STEAM-5 454 3.70 1.00 0 3.00 3.00 0 0 0 0 0 0 0 0

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Table 4-35. Waste CODP Streams First pre-heating train WAT-SP20 Temperature(C) 76.1 Pressure (bar_a) 1.70 Mass Vapor Fraction 0 Mass Liquid Fraction 1.00 Total Flow (ton/h) 3.80 Component mass flow (ton/h) Water 3.80 Propane 0 Isobutane 0 N-Butane 0 Isopentane 0 N-Pentane 0 N-Hexane 0 Pseudocomponents 0 Atmospheric Unit Vacuum unit WATSP203 GAST4 WAT-S204 98.3 97.8 48.9 1.70 1.70 1.20 0 1.00 0 1.00 0 1.00 1.60 11.3 3.00 1.60 0 0 0 0 0 0 0 2.10 0.100 0.100 0.200 0.400 0.300 0.400 7.70 3.00 0 0 0 0 0 0 0

- Heat integration Appendix D shows a literature review of heat integration. The base case for CODP resulted in energetic requirements for heating of 126 GJ/h, and for cooling of 129 GJ/h. With the current equipment, it was not possible to make low cost energy integration, because new equipment was required. Furthermore, it was not possible to make power integration because CODP do not have power generation equipment. - Cost analysis Cost analysis for CODP was made in the base case, regardless the inclusion of new equipment and made integrations (mass, heat) in the process. For this process, it is not necessary to make a capital investment because it is supposed that CODP plant was already in operation. However, capital investment was calculated in order to estimate the FCI. This

82

value is necessary to obtain the FOC. Table 4-36 shows the FCI obtained. Where, atmospheric unit represent the highest cost with 50.9% because all heating and cooling equipment associated, mainly the furnace and the tower cost. Table 4-365. FCI for CODP in base case 1st-Pre-heating train 2nd-Pre-heating train Atmospheric unit Vacuum unit Total FCI % FCI 11.8 9.30 50.9 27.9 100 TOTAL FCI (USD) 2,165,988 1,709,220 9,336,879 5,117,311 18,329,399

Table 4-37 shows the VOC for CODP. The total VOC is 838,572,493 USD per year. This obtained cost is higher than cost obtained for MixAlco process, because the crude oil price is 93.6 USD per barrel (643 USD/ton), represented the 99.4% of total VOC. Although, utilities represent 0.6% of total VOC, this amount 5,097,185 USD/ year. Table 4-37. VOC of CODP in base case
Rate Feedstock Crude oil Utility Fired Heat LP Steam Cooling Water Steam @ 353C Steam @ 454C Electricity Total VOC 162 ton/h 201.3 2.20 6,151.4 4.00 3.00 0.28 ton/h ton/h m3/h ton/h ton/h MW Prices 643 USD/ton 2.50 USD/ton 4.20 USD/ton 0.00400 USD/m3 10.0 USD/ ton 10.0 USD/ ton 0.0620 USD/kWh Annual cost (USD) 833,475,308 4,105,591 74,480 218,234 320,000 240,000 138,880 838,572,493

The number of total operators was calculated for four process zones. Each of them was established to need two operators. This resulted in a total of eight operators per shift;

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and the total shifts are five due to illness, vacations, holidays, training, and overtime during startups. The labor, maintenance and overhead operating cost accounts were based on (Seider, Seader, & Lewin, 2004) (Peters, Timmerhaus, & West, 2004). The plant operating hours were established as 8000 per year. The FOC obtained for CODP was calculated in USD 5,976,964. Table 4-38 shows the FOC for this process in detail. The labor was the highest cost represented in 61.3% of total FOC, following to labor that represents 24.7% of total FOC, while operating overhead represent 14% of total FOC. Table 4-38. FOC for CODP in base case Annual cost (USD) Labor Direct wage and benefits (DW&B) Direct salary and benefits Operating supplies and services Technical asistants to manufacturing control laboratory Maintenance Wages and benefits (MW&B) Salaries and benefits Materials and services Maintenance overhead Operating overhead General plant overhead Mechanical department services Employee relations department Business services Total FOC 2,496,000 374,400 149,760 416,000 228,000 641,529 160,382 641,529 32,076 260,734 88,135 216,666 271,751 5,976,964

To verify the analysis cost of CODP was supposed as a new plant. The obtained ROI was 31.2% and the NPV was MM USD 29.

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4.3.2 Internal modification The second loop of the proposed methodology covers only internal modifications adding new units in each plant. With the aim of apply this second step, replacements and additions of new equipments for MixAlco process and CODP were made. 4.3.2.1 MixAlco process - Mass integration As explained before (Section 4.3.1.1) mass integration using the resulting impurityfree water from dewatering and gasification process is the only possibility accounted for in this work. - Heat integration In the MixAlco process, some streams could not be energetically integrated because these are needed in the power generation from gasification unit. Also, some streams are needed in the heat exchanger arrangements in the dewatering process. Table 439 shows the hot and cold streams used for the energy integration.

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The streams to be cooled were labeled as hot (H), the total streams are 16, meanwhile the streams to be heated were labeled as cold (C), the total streams are 16. Besides, Table 4-39 shows inlet and outlet temperatures, the mass and heat capacity (MCp), the flow rate and the enthalpy of the streams. The heating and cooling utility load required for the base case was 4.33x10 8 kJ/h and 8.21x107 kJ/h, respectively. Table 4-39. MixAlco process streams for HEN
Service H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 H15 H16 C1 Inlet T Outlet T (C) (C) 130 430 961 500 961 400 266 408 254 162 268 55 55 55 50 162 150 55 -15 130 55 130 130 25 25 43 94 266 46 46 46 41 60 165 MCp (kJ/C-h) 5.61x103 2.93x104 5.10x103 4.21x103 1.67x103 2.65x104 1.94x104 7.02x103 2.90x104 1.79x105 9.83x104 8.05x105 8.05x105 8.04x105 7.96x105 5.02x106 4.51x106 Enthalpy (kJ/h) 4.21x105 1.31x107 4.24x106 1.87x106 1.39x106 7.15x106 4.68x106 2.69x106 6.11x106 1.21x107 1.97x105 7.00x106 7.01x106 7.03x106 7.06x106 5.12x108 6.83x107 Flowrate (kg/h) 6.30x103 9.59x103 3.40x102 4.06x103 1.11x102 7.37x103 5.28x103 2.09x103 2.28x104 5.00x103 5.28x103 2.00x105 2.00x105 2.00x105 2.00x105 2.01x105 3.34x104 Name PRET-FER.CACO3REC_To_PRET-FER.CACO3 KETONIZA.KET-CACO_To_KETONIZA.KT-CACO3 KETONIZA.H21_To_KETONIZA.H2-1 LIME-KIL.CAO_To_LIME-KIL.CAO-CO2 FINAL.H2-_To_FINAL.H2-1 FINAL.OLF_To_FINAL.OLEFIN FINAL.HC-C4--8_To_FINAL.LIGHT FINAL.HC-C9-12_To_FINAL.HEAVY GASIFICA.C+H2+H20_To_GASIFICA.H2+ GASIFICA.STEAMSAT_To_GASIFICA.WATER FINAL. CONDENSER T-101 PRET-FER.SALT3_To_PRET-FER.SALW1 PRET-FER.SALT4_To_PRET-FER.SALW3 PRET-FER.SALT5_To_PRET-FER.SALW5 PRET-FER.H20-FERM_To_PRET-FER.H2O DEWATER.WATER_To_DEWATER.WATDISTI DEWATER.SALWR1_To_DEWATER.SALWR7

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Service C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C16

Inlet T Outlet T (C) (C) 150 150 150 150 150 163 -15 130 130 289 55 165 165 165 165 164 430 130 300 500 408 150

MCp (kJ/C-h) 4.51x106 4.51x106 4.51x106 4.51x106 4.84x106 7.86x103 2.25x104 5.33x104 9.61x103 4.65x104 5.39x106

Enthalpy (kJ/h) 6.83x107 6.83x107 6.83x107 6.83x107 6.84x107 2.10x106 3.26x106 9.05x106 3.55x106 5.53x106 5.12x108

Flowrate (kg/h) 3.34x104 3.34x104 3.34x104 3.34x104 3.34x104 2.52x104 9.59x103 9.93x103 9.20x103 2.09x103 2.00x105

Name DEWATER.SALWR2_To_DEWATER.SALWR8 DEWATER.SALWR3_To_DEWATER.SALWR9 DEWATER.SALWR4_To_DEWATER.SALWR10 DEWATER.SALWR5_To_DEWATER.SALWR11 DEWATER.SALWR6_To_DEWATER.SALWR12 KETONIZA.SAL-DEH_To_KETONIZA.SALT KETONIZA.KT-CACO3_To_KETONIZA.KET KETONIZA.ALCOHOL_To_KETONIZA.OH LIME-KIL.CACO3-2_To_LIME-KIL.CACO3-3 FINAL. REBOILER T-101 DEWATER.SAL-DESC_To_DEWATER.SALT-H20

The hot and the cold curves composite are shown in Figure 4-21, where a hot pinch temperature was 60.5C, and cold pinch temperature was 55C. The grand composite curve is shown in Figure 4-22, where the pinch temperature is shown when the net heat flow in the process is zero.

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Pinch point

Figure 4-21. Hot and Cold composite for MixAlco HEN

Pinch point

Figure 4-22. Grand composite curve for MixAlco HEN

Heat integration was made using two HEN cases with a Tmin of 2C and 5.5C; and one optimized case Minimizing Total Annualized Cost (MTAC) based on the case of Tmin = 5.5C, for a total of three study cases. Table 4-40 shows the heat integration results of these cases and the base case.

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For MixAlco process, the best heat integration resulted with the optimized case when a Tmin = 5.5C was used. For heat integration, the hot utilities used were fired heat, MP steam and LP steam. By the other hand, the cooling utilities used were cooling water and refrigerant. The optimum arrangement whit the MTAC, resulted in a heating load of 4.19 x108 kJ/h and a cooling load of 6.85 x107 kJ/h. It results reduced in 8.3% the capital cost and in 8.6% the operating cost compared to the base case. Table 4-40. Heat integration for MixAlco process
Base case HEN proposed (with integration) T (2C) T (5.5C) 7.99x106 7.99x106 4.11x108 4.08x108 7 6.65x10 6.65x107 0 2.70x106 2.00x106 2.01x106 4.19x108 4.19x108 6.85x107 6.85x107 1.40 x107 1.32 x107 7.66x106 7.65x106 Optimized MTAC T (5.5C) 7.99x106 4.08x108 6.74x107 2.70x106 1.10x106 4.19x108 6.85x107 1.34 x107 7.64x106 Target

Fired Heat (kJ/h) MP Steam (kJ/h) Cooling Water (kJ/h) LP Steam (kJ/h) Refrigerant (kJ/h) Heating (kJ/h) Cooling (kJ/h) Capital cost (USD) Operating cost (USD/year)

2.02x10 4.13x108 6.90x107 0 1.31x107 4.33x108 8.21x107 1.44x107 8.36x106

7.09x106 4.11x108 6.65x107 0 1.15x106 3.83x108 3.29x107 2.91x107 6.78x106

Figure 4-23 shows the grid diagram that indicates the configuration of the heat exchangers between the streams in the MixAlco process. Also, it shows the utilities streams for heaters and coolers in the best arrangement. Table 4-41 to 4-43 show the worksheets of each heat exchangers, heaters and coolers including the temperature of each stream, the area and the heat load.

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The required heat exchangers are 9, with a total heat load of 5.26x108 kJ/h. The required heaters are 11 for a total heating load of 4.19x108 kJ/h. And, the required coolers are 15 for a total cooling load of 6.85x107 kJ/h.

Figure 4-23. Grid diagram for MixAlco HEN

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Table 4-41. Heat exchangers for MixAlco HEN

Heat Exch Cold Stream Cold T in (C) 289 130 55 289 130 331 55 55 150 Cold T out (C) 331 300 150 331 300 359 55 150 165 Hot Stream KETONIZA.KETCACO_To_KETONIZA.KT-CACO3 KETONIZA.KETCACO_To_KETONIZA.KT-CACO3 DEWATER.WATER_To_DEWATE R.WATDISTI FINAL.OLF_To_FINAL.OLEFIN FINAL.OLF_To_FINAL.OLEFIN FINAL.OLF_To_FINAL.OLEFIN FINAL.OLF_To_FINAL.OLEFIN GASIFICA.STEAMSAT_To_GASIFI CA.WATER KETONIZA.KETCACO_To_KETONIZA.KT-CACO3 Hot T in (C) 362 309 162 351 336 400 145 162 430 Hot T out (C) 309 173 60 336 145 351 130 94 362 Load (kJ/h) 1.55x106 3.99x106 4.99x108 3.89x10 5.06x10 1.30x10
5 6 6

Area (m2) 123 116 9,326 23 141 80 2 72 3

E-141 FINAL.REBOILER T-101 E-143 KETONIZA.ALCOHOL_To_KETONIZA.OH DEWATER.SALE-116 DESC_To_DEWATER.SALT-H20 E-140 FINAL.REBOILER T-101 E-142 KETONIZA.ALCOHOL_To_KETONIZA.OH E-139 FINAL.REBOILER T-101 DEWATER.SALE-148 DESC_To_DEWATER.SALT-H20 DEWATER.SALE-115 DESC_To_DEWATER.SALT-H20 DEWATER.SALWR3_To_DEWATER.SAL E-117 WR9

3.95x105 1.21x107 2.00x106

Table 4-42. Coolers for MixAlco HEN

Heat Exchanger E-132 E-136 E-133 E-127 E-125 E-147 Utility Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Hot Stream DEWATER.WATER_To_DEWATER.WATDISTI FINAL.HC-C9-12_To_FINAL.HEAVY FINAL.HC-C4--8_To_FINAL.LIGHT FINAL.H2-_To_FINAL.H2-1 PRET-FER.SALT4_To_PRET-FER.SALW3 KETONIZA.KET-CACO_To_KETONIZA.KT-CACO3 Hot T in (C) 162.1 407.8 266.2 961.0 55.0 173.0 Hot T out (C) 60.0 25.0 25.0 130.0 46.3 53.1 Load (kJ/h) 1.33x107 2.69x106 4.68x106 1.39x106 7.01x106 3.52x106 Area (m2) 22.7 12.0 28.3 2.70 33.5 15.7

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Heat Exchanger E-149 E-126 E-130 E-128 E-138 E-146 E-135 E-131 E-129

Utility Refrigerant 1 Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water

Hot Stream KETONIZA.KET-CACO_To_KETONIZA.KT-CACO3 PRET-FER.CACO3REC_To_PRET-FER.CACO3 GASIFICA.C+H2+H20_To_GASIFICA.H2+ KETONIZA.H21_To_KETONIZA.H2-1 FINAL.CONDENSER T-101 PRET-FER.SALT3_To_PRET-FER.SALW1 LIME-KIL.CAO_To_LIME-KIL.CAO-CO2 PRET-FER.SALT5_To_PRET-FER.SALW5 PRET-FER.H20-FERM_To_PRET-FER.H2O

Hot T in (C) 53.1 130.0 254.0 961.0 268.0 55.0 500.0 55.0 50.0

Hot T out (C) -15.2 55.0 43.0 130.0 266.0 46.3 55.0 46.3 41.1

Load (kJ/h) 2.01x106 4.21x105 6.11x106 4.24x106 1.97x105 7.00x106 1.87x106 7.03x106 7.06x106

Area (m2) 30.3 9.90 798.5 8.30 1.20 30.4 138.1 33.6 42.0

Table 4-436. Heaters for MixAlco HEN

Heat Exchanger E-137 E-145 E-134 E-122 E-124 E-120 E-118 E-123 E-119 E-121 E-144 Utility LP Steam Fired Heat Fired Heat MP Steam MP Steam MP Steam MP Steam MP Steam MP Steam MP Steam Fired Heat Cold Stream KETONIZA.KT-CACO3_To_KETONIZA.KET KETONIZA.SAL-DEH_To_KETONIZA.SALT FINAL.REBOILER T-101 KETONIZA.KT-CACO3_To_KETONIZA.KET DEWATER.SALWR4_To_DEWATER.SALWR10 DEWATER.SALWR1_To_DEWATER.SALWR7 DEWATER.SALWR5_To_DEWATER.SALWR11 DEWATER.SALWR3_To_DEWATER.SALWR9 DEWATER.SALWR6_To_DEWATER.SALWR12 DEWATER.SALWR2_To_DEWATER.SALWR8 LIME-KIL.CACO3-2_To_LIME-KIL.CACO3-3 Cold T in (C) -15 163 359 105 150 150 150 150 150 150 130 Cold T out (C) 105 430 408 130 165 165 165 165 164 165 500 Load (kJ/h) 2.70x106 2.10x106 2.29x106 5.55x105 6.83x107 6.83x107 6.83x107 6.63x107 6.84x107 6.83x107 3.55x106 Area (m2) 11.0 35.0 17.0 2.00 297 297 297 289 283 297 50.0

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- Cost analysis The total VOC is shown in Table 4-44 for MixAlco process with the above integrations resulted in 35,770,884 USD per year. The VOC saving was achieved in 1.98% per year, compared to the base case. The mainly difference with the base case is a new consumption of LP steam, and the reduction of fire heat in 60.5% and refrigerant in 91.6%. Table 4-44. VOC of MixAlco process with HEN Rate Feedstock Sugarcane baggase Manure Chemical Lime Flocculant Iodoform CaCO3 Utility Fired Heat MP Steam Cooling Water LP Steam Refrigerant Electricity Material disposal Total VOC 32.0 ton/h 8.00 ton/h 0.900 10.0 3.20 9.00 13.318 206.062 3,224.817 1.231 228.313 13.0 6.00 ton/h kg/h kg/h ton/h ton/h ton/h m3/h ton/h m3/h MW ton/h Prices 60.0 USD/ton 10.0 USD/ton 70.0 USD/ton 991 USD/ton 25.0 USD/kg 50.0 USD/ton 2.50 USD/ton 4.40 USD/ton 0.00400 USD/m3 4.20 USD/ton 0.0131 USD/ m3 0.0620 USD/kWh 18.0 USD/ton Annual cost (USD) 15,360,000 640,000 504,000 79,280 640,000 3,600,000 271,630 7,184,465 114,407 41,090 24,011 6,448,000 864,000 35,770,884

The FOC obtained for MixAlco process resulted in 15,498,900 USD per year. Table 4-45 shows the FOC obtained in detail. The FOC saving was achieved in 0.63% per year, compared to the base case. The variations were obtained in maintenance and operating overhead; the labor did not change.

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The total FCI obtained for this process was USD 111,640,076, in this value the capital cost saving for HEN integration was discount; reducing the FCI in 0.96% compared with the base case. The WCI was calculated as 10% of FCI, with a total of USD 11,164,008. The TCI was calculates as the sum of WCI and FCI, resulting in USD 122,804,084. Table 4-45. FOC of MixAlco process with HEN Annual cost (USD) Labor Direct wage and benefits (DW&B) Direct salary and benefits Operating supplies and services Technical asistants to manufacturing control laboratory Maintenance Wages and benefits (MW&B) Salaries and benefits Materials and services Maintenance overhead Operating overhead General plant overhead Mechanical department services Employee relations department Business services 3,120,000 468,000 187,200 520,000 285,000 3,907,403 976,851 3,907,403 195,370 601,530 203,334 499,863 626,947 15,498,900

Table 4-46 shows the obtained profitability results for MixAlco process with and without the time value of money.

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Table 4-46. Summary MixAlco economic results with HEN Parameter Profitability without the time value of money ROI estimated (%) Annual gross (pre tax) profit (USD) Annual net (after tax) profit (USD) PBP (years) Total operating cost (USD) FCI (USD) WCI (USD) TCI (USD) Profitability with the time value of money NPV (USD) ROI real (%) Annual sales (USD) Tax rate (%) Discount rate (%) Value 15.65 21,607,790 17,477,107 4.23 51,269,784 111,640,076 11,164,008 122,804,084 11,722,637 11.809 72,877,573 35.0 10.0

The MixAlco process integration results in a ROI of 11.8% acceptable in current market conditions, a ROI increment of 0.68% was obtained compared with the base case. The NPV represent a profitable project in USD 11,722,637, with a NPV increment of 37.8% compared with the base case. The PBP is about 4.23 years after start of operation. The cumulative discounted cash flow for this case is shown in the Figure 4-24. This shown that after paying all the expenses of the project, the revenues of the project will give net value of MM USD 11.7 in the present dollars.

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Figure 4-24. Cash flow for MixAlco process with HEN

4.3.2.2 CODP - Mass integration According to section 4.3.1.2, there is not possible to make a mass integration for CODP. - Heat integration Table 4-47 shows the hot and cold streams of the process available to make the heat integration. The streams to be cooled were labeled as hot (H), the total streams are 15, meanwhile the streams to be heated were labeled as cold (C), the total streams are 7. Also, it shows the inlet and outlet temperatures, the mass and heat capacity (MCp), the flow rate and the enthalpy of the streams in CODP.

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Table 4-47. Process streams for CODP

Service H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 H15 C1 C2 C3 C4 C5 C6 C7 Inlet T (C) 144 236 324 390 289 277 193 284 304 144 213 60 143 285 324 31 44 183 228 148 98 366 Outlet T MCp (C) (kJ/C-h) 44 138 75 285 236 227 68 148 288 98 34 49 49 169 233 181 76 277 381 279 98 432 4.17x105 2.16x105 8.91x104 1.29x105 2.37x105 4.28x105 4.64x104 1.35x105 1.29x105 4.45x105 1.14x104 6.52x105 8.10x104 1.82x105 8.69x103 3.46x105 1.51x105 4.16x105 5.14x105 1.35x105 7.21x104 3.66x105 Enthalpy (kJ/h) 4.19x107 2.13x107 2.22x107 1.35x107 1.25x107 2.15x107 5.81x106 1.84x107 2.03x106 2.08x107 2.04x106 7.24x106 7.62x106 2.11x107 7.87x105 5.22x107 4.87x106 3.90x107 7.87x107 1.77x107 3.44x104 2.44x107 Flowrate (kg/h) 6.48x104 8.80x104 3.69x104 4.66x104 8.80x104 1.62x105 1.99x104 5.29x104 4.62x104 6.48x104 5.26x103 3.00x103 3.85x104 7.20x104 3.24x103 1.62x105 6.48x104 1.62x105 1.62x105 5.29x104 4.40x103 8.88x104 Name 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 1-TRAIN.DIE203_To_1-TRAIN.DIEST204 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 2-TRAIN.ASFP205_To_2-TRAIN.ASPHALT 2-TRAIN.DIEST204_To_2-TRAIN.DISE205 ATM-UNIT.SP-202_heat ATM-UNIT.JETT204_To_ATM-UNIT.JET-T204 MPA_Draw@ATM-UNIT.T-204_To_MPA_Return@ATM-UNIT.T-204 MPACAL_Draw@ATM-UNIT.T-204_To_MPACAL_Return@ATMUNIT.T-204 To Condenser@ATM-UNIT.T-204_TO_ATM-UNIT.NAPHT204 VAC-UNIT.LVGOT205_To_VAC-UNIT.LVGO-205 VAC-UNIT.SP-204_heat UPA_Draw@VAC-UNIT.T-205_To_UPA_Return@VAC-UNIT.T-205 MPA_Draw@VAC-UNIT.T-205_To_MPA_Return@VAC-UNIT.T-205 MPACAL_Draw@VAC-UNIT.T-205_To_MPACAL_Return@VACUNIT.T-205 1-TRAIN.CRUDE-IN_To_1-TRAIN.CRDTP1 1-TRAIN.SP-201_heat 2-TRAIN.CRDTP1R_To_2-TRAIN.CRDE207 ATM.UNIT.FURNACE ATM-UNIT.MPAT204_To_ATM-UNIT.MPAM201 ATM-UNIT.SP-203_heat VAC-UNIT.CRDT204_To_VAC-UNIT.CREDT205

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The hot and the cold curves composite are shown in Figure 4-25, where a hot pinch temperature was 277.2C, and cold pinch temperature was 271.8C. The grand composite curve is shown in Figure 4-26 where the pinch temperature is shown when the net heat flow in the process is zero.

Pinch point

Figure 4-25. Hot and Cold composite for CODP HEN

Pinch point

Figure 4-26. Grand composite curve for CODP HEN

The heat integration was made using two HEN cases with a Tmin of 4C and 5.35C, and two optimized cases based on the case of Tmin = 5.35C one to optimized the

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MTAC and the other, to optimize de minimum heat area, for a total of four cases. Table 448 shows the heat integration results of these cases and the base case. For CODP, the best heat integration resulted when optimized the MTAC and Tmin= 5.3C was used. In CODP heat integration, the hot utilities used were fired heat and LP steam. By the other hand, the cooling utility used was cooling water. The heating and cooling utility load required for the base case was 1.26 x108kJ/h and 1.29x108kJ/h, respectively. The optimum arrangement whit the MTAC resulted in a heating load of 7.45 x107 kJ/h and a cooling load of 7.65 x107 kJ/h. It results reduced in 39% the operating cost, but increased in 78% the capital cost compared with the base case. Table 4-48. Summary of HEN cases for CODP
Base case HEN proposed Optimized Optimized (with integration) MTAC Min Area T T T T (5.35C) (4C) (5.35C) (5.35C) 7.33x107 7.36x107 7.45x107 7.33x107 7.53x107 7.56x107 7.65x107 7.53x107 3.44x104 3.44x104 3.44x104 3.44x104 7.34x107 7.37x107 7.45x107 7.34x107 7.53x107 7.56x107 7.65x107 7.53x107 1.81x107 1.93x107 1.51x107 1.67x107 2.62x106 2.63x106 2.66x106 2.62x106 Target

Fired Heat (kJ/h) Cooling Water (kJ/h) LP Steam (kJ/h) Heating (kJ/h) Cooling (kJ/h) Capital cost (USD) Operating cost (USD/year)

1.21x108 1.29x108 4.90x106 1.26x108 1.29x108 8.50x106 4.40x106

5.85x107 6.04x107 4.61x107 1.91x106

Figure 4-27 shows the grid diagram that indicates the configuration of the heat exchangers between the streams in the CODP. Also, it shows the utilities streams arrangements.

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Table 4-49 to 4-51 show the worksheets of each heat exchangers, heaters and coolers including the temperature of each stream, the area and the heat load. The required heat exchangers are 24, with a total heat load of 1.42x108 kJ/h. The required heaters are 3 for a total heating load of 7.45x107 kJ/h. And, the required coolers are 6 for a total cooling load of 7.65x107kJ/h.

Figure 4-27. Grid diagram for CODP HEN

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Table 4-49. Heat exchangers in the best CODP case

Heat Exch E-148 E-133 E-135 E-149 E-126 E-128 E-134 E-136 E-118 E-140 E-137 E-139 E-129 E-127 E-131 E-125 Cold Stream 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 ATM.UNIT.FURNACE 1-TRAIN.CRUDE-IN_To_1TRAIN.CRDTP1 1-TRAIN.SP-201_heat 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 ATM-UNIT.MPAT204_To_ATMUNIT.MPAM201 ATM.UNIT.FURNACE 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 ATM-UNIT.MPAT204_To_ATMUNIT.MPAM201 1-TRAIN.CRUDE-IN_To_1TRAIN.CRDTP1 1-TRAIN.CRUDE-IN_To_1TRAIN.CRDTP1 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 1-TRAIN.CRUDE-IN_To_1TRAIN.CRDTP1 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 Cold T in (C) 183 228 69 44 207 242 228 207 259 148 31 31 207 207 96 207 Cold T out (C) 207 256 96 76 262 257 259 207 281 230 82 60 232 257 120 268 Hot Stream ATM-UNIT.SP-202_heat ATM-UNIT.SP-202_heat MPA_Draw@ATM-UNIT.T204_To_MPA_Return@ATM-UNIT.T-204 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 2-TRAIN.DIEST204_To_2-TRAIN.DISE205 MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 MPACAL_Draw@ATM-UNIT.T204_To_MPACAL_Return@ATM-UNIT.T204 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 ATM-UNIT.JETT204_To_ATM-UNIT.JETT204 ATM-UNIT.SP-202_heat 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 MPACAL_Draw@VAC-UNIT.T205_To_MPACAL_Return@VAC-UNIT.THot T Hot T in out (C) (C) 250 274 216 188 273 285 275 252 304 251 239 193 277 267 144 324 227 250 148 95 236 275 241 251 288 188 121 68 274 252 124 233 Load (kJ/h) 9.73x106 1.06x107 9.19x106 4.87x106 8.86x106 1.94x106 4.49x106 9.64x104 2.03x106 5.61x106 7.57x106 5.81x106 1.21x106 1.36x106 8.37x106 7.87x105 Area (m2) 405 1605 103 132 320 41 600 2 52 184 74 92 38 52 386 15

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Heat Exch

Cold Stream

Cold T in (C) 259 120 148 257 228 207 259 257

Cold T out (C)

Hot Stream 205

Hot T Hot T in out (C) (C) 324 236 239 390 275 284 289 324 268 138 195 285 234 216 273 267

Load (kJ/h)

Area (m2)

E-121 E-119 E-141 E-130 E-132 E-124 E-120 E-122

2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 1-TRAIN.CRUDE-IN_To_1TRAIN.CRDTP1 ATM-UNIT.MPAT204_To_ATMUNIT.MPAM201 ATM.UNIT.FURNACE ATM-UNIT.MPAT204_To_ATMUNIT.MPAM201 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 2-TRAIN.CRDTP1R_To_2TRAIN.CRDE207 ATM-UNIT.MPAT204_To_ATMUNIT.MPAM201

277 181 226 283 242 263 275 279

2-TRAIN.HVGO_To_2-TRAIN.GPVT205 1-TRAIN.DIE203_To_1-TRAIN.DIEST204 MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 2-TRAIN.ASFP205_To_2-TRAIN.ASPHALT MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 MPA_Draw@ATM-UNIT.T204_To_MPA_Return@ATM-UNIT.T-204 2-TRAIN.DIEST204_To_2-TRAIN.DISE205 2-TRAIN.HVGO_To_2-TRAIN.GPVT205

2.03x106 2.13x107 5.22x106 1.35x107 1.93x106 9.22x106 3.66x106 3.02x106

84 773 133 534 86 473 163 122

Table 4-50. Coolers in the best CODP case

Heat Exchanger E-150 E-144 E-146 E-151 E-145 E-143 Utility Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Hot Stream 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 VAC-UNIT.LVGOT205_To_VAC-UNIT.LVGO-205 To Condenser@ATM-UNIT.T-204_TO_ATM-UNIT.NAPHT204 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 UPA_Draw@VAC-UNIT.T-205_To_UPA_Return@VAC-UNIT.T205 VAC-UNIT.SP-204_heat Hot T in (C) 124 213 144 188 143 60 Hot T out (C) 44 34 98 45 49 49 Load (kJ/h) 3.36x107 2.04x106 2.08x107 5.22x106 7.62x106 7.24x10
6

Area (m2) 229 18 95 43 55 349

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Table 4-51. Heaters in the best CODP case

Heat Exchanger E-123 E-147 E-142 Utility Fired Heat LP Steam Fired Heat Cold Stream ATM.UNIT.FURNACE ATM-UNIT.SP-203_heat VAC-UNIT.CRDT204_To_VACUNIT.CREDT205 Cold T Cold T in (C) out (C) 283 98.0 366 381 98.0 432 Load (kJ/h) 5.01x107 3.44x104 2.44x107 Area (m2) 450 2.00 1,001

Cost analysis

The total VOC for CODP was shown in Table 4-52 with the above integrations resulted in USD 836,837,003 per year. The VOC saving was achieved in 1,735,491 USD per year. The FOC for CODP did not change for the base case, because the operators number and salaries kept equal. Although VOC saving was achieved, a capital cost must be assumed for installation of new heaters, coolers and heat exchangers. Table 4-527. VOC of CODP with HEN Rate Feedstock Crude oil Utility Fired Heat LP Steam Cooling Water Steam @ 353C Steam @ 454C Electricity Total VOC 162 ton/h 124.2 0.0160 3,656.8 4.00 3.00 0.280 ton/h ton/h m3/h ton/h ton/h MW Prices 643 USD/ton 2.50 USD/ton 4.20 USD/ton 0.00400 USD/m3 10.0 USD/ ton 10.0 USD/ ton 0.062 USD/kWh Annual cost (USD) 833,475,308 2,532,560 523 129,731 320,000 240,000 138,880 836,837,003

This new capital cost was USD 15,010,866. CODP integration results in a ROI of 41.8% and a NPV of MM USD 39.165. To compare the convenience of heat integration

103

into CODP, the profitability of CODP integrated as a new plant was evaluated, as in the base case. The results show that CODP integration had a reduction of ROI in 3.5%, but a NPV increment in MM USD 2.7 was obtained compared to the base case.

4.3.3 External modification The third loop of the proposed methodology covers only external modifications adding new production lines for linkage (retrofitting analysis) between MixAlco process and CODP (Figure 4-28). With the aim of applying this third step, additions of new production lines for the linkage were made. Due to assumption that CODP plant was already in operation, MixAlco was added as a new production line in the CODP. Mass integration

The mass integration was performed as suggested in Section 4.3.1.1, that is, using the resulting impurity-free water from the dewatering and gasification inside MixAlco process. Additionally, no other opportunity for integration was identified because calcium carbonate (the other fresh stream required in MixAlco process) is not involved in any of the operations of CODP. However, considered the water demand in feed handling process (for quick lime hydration); and water lost in pretreatment and fermentation process.

104

Figure 4-28. MixAlco and CODP simulation integrated

It was possible to make a mass integration between both processes through the water (waste impurity-free water from CODP and needed water in feed handling, fermentation and pretreatment). The material water disposal in the MixAlco process was around 6 ton/h, with a treatment cost of 18USD/ton. This resulted in a total operating cost of 864,000 USD per year. Through the mass integration made, the material disposal cost was saved. Additionally, a FCI saving was achieved in USD 148,598 for the purchased equipment and installation of this process.

105

On the other hand, integration of the biomass feedstock into the CODP was not useful because units required for treating the biomass are not available in the CODP. Heat integration

It was possible to establish two heat integration cases. The first case was related to integration of the remaining streams for both processes after heat integration within each plant. The second case was related to integration between the remaining streams of CODP after heat integration within the plant, and the base case of MixAlco process. 4.3.3.1 Case 1. The first case was integration between MixAlco process and CODP after heat integration within each plant, and evaluating the retrofitting analysis of the linkage. - Heat integration The heat integration in this case is joining the results in numerals 4.3.2.1 for MixAlco process with the results in numeral 4.3.2.2 for CODP. The heating and cooling utility load required for the both plants was 5.59x108 kJ/h and 2.11x108 kJ/h, respectively. The optimum arrangement whit the MTAC, resulted in a heating load of 4.94 x108 kJ/h and a cooling load of 1.45 x108 kJ/h. It results reduced in 24.1% the operating cost and increased in 19.1% the capital cost compared with the base case (Table 4-53). For the retrofitting analysis 33 heat exchangers are needed, 14 heaters and 21 coolers.

106

Table 4-53. Heat integration for MixAlco and CODP in case 1 Base case joining both plants 1.41x108 4.13x108 1.98x108 4.90x106 1.31x107 5.59x108 2.11x108 2.29x107 1.28x107 MixAlco with internal HEN 7.99x106 4.08x108 6.74x107 2.70x106 1.10x106 4.19x108 6.85x107 1.32x107 7.63x106 CODP with internal HEN 7.45x107 0 7.65x107 3.44x104 0 7.45x107 7.65x107 1.51x107 2.65x106 MixAlco and CODP case 1 8.25x107 4.08x108 1.44x108 2.73x106 1.10x106 4.94x108 1.45x108 2.83x107 1.03x107

Case 1 Fired Heat (kJ/h) MP Steam (kJ/h) Cooling Water (kJ/h) LP Steam (kJ/h) Refrigerant (kJ/h) Heating (kJ/h) Cooling (kJ/h) Capital cost (USD) Operating cost (USD/year)

Cost analysis Table 4-54. VOC of MixAlco process in case 1 Rate Prices 60.0 USD/ton 10.0 USD/ton 70.0 USD/ton 991 USD/ton 25.0 USD/kg 50.0 USD/ton 2.50 USD/ton 4.40 USD/ton 0.00400 USD/m3 4.20 USD/ton 0.0131 USD/ m3 0.0620 USD/kWh Annual cost (USD) 15,360,000 640,000 504,000 79,280 640,000 3,600,000 271,630 7,184,465 114,407 41,090 24,011 6,448,000 34,906,884

Feedstock Sugarcane baggase Manure Chemical Lime Flocculant Iodoform CaCO3 Utility Fired Heat MP Steam Cooling Water LP Steam Refrigerant Electricity Total VOC

32.0 ton/h 8.00 ton/h 0.900 10.0 3.20 9.00 13.3 206 3,224 1.23 228 13.0 ton/h kg/h kg/h ton/h ton/h ton/h m3/h ton/h m3/h MW

107

The total VOC for MixAlco process with the above integrations resulted in 34,906,884 USD per year, with a reduction of 4.55%, compare with the base case. Table 454 shows the VOC in detail. The total VOC for CODP is the same obtained in numeral 5.3.2.2 (836,837,003 USD per year), with a reduction in 0.21%, compare with the base case. The FOC obtained for MixAlco process resulted in 15,485,455 USD per year; with a reduction of 0.72%, compare with the base case. The FOC for CODP did not change for the base case, because the operators number and salaries kept equal. Table 4-55 shows a compiled FOC obtained for MixAlco and CODP. Table 4-558. FOC of MixAlco and CODP in case 1 Annual cost (USD) MixAlco Labor Direct wage and benefits (DW&B) Direct salary and benefits Operating supplies and services Technical asistants to manufacturing control laboratory Maintenance Wages and benefits (MW&B) Salaries and benefits Materials and services Maintenance overhead Operating overhead General plant overhead Mechanical department services Employee relations department Business services Total FOC 3,120,000 468,000 187,200 520,000 285,000 3,902,202 975,550 3,902,202 195,110 601,068 203,178 499,479 626,466 15,485,455

CODP 2,496,000 374,400 149,760 416,000 228,000 641,529 160,382 641,529 32,076 260,734 88,135 216,666 271,751 5,976,964

108

The total FCI obtained for MixAlco process is USD 111,491,478; in this value capital costs savings for mass and heat integration were discount; resulting in a reduction of 1.10% compared with the base case. The WCI was USD 11,149,148, and the TCI results in USD 122,640,626. The total FCI for CODP is USD 15,010,866, because an investment is required for the new heat equipment arrangement. In CODP possible revenue from selling heat equipment to be replaced, was no accounted. Table 4-56 shows the obtained profitability results for MixAlco process and CODP, with and without the time value of money applying the integration mentioned in this numeral. Table 4-56. Summary MixAlco economic results in case 1
MixAlco with integration Value Profitability without the time value of money ROI estimated (%) Annual gross (pre tax) profit (USD) Annual net (after tax) profit (USD) PBP (years) Total operating cost (USD) FCI (USD) WCI (USD) TCI (USD) 16.47 22,485,234 18,360,049 3.55 50,392,339 111,491,478 11,149,148 122,640,626 72.49 11,437,226 10,881,824 1.19 842,813,966 15,010,866 1,501,087 16,511,953 CODP with integration Value

Parameter

Profitability with the time value of money NPV (USD) ROI real (%) Annual sales (USD) Tax rate (%) Discount rate (%) 15,699,518 12.4 72,877,573 35 10 39,165,307 41.8 854,251,193 35 10

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The retrofitting analysis in case 1 for MixAlco process results in a ROI of 12.4% acceptable in current market conditions; a ROI increment in 1.3% compared with the base case. The NPV represent a profitable project in MM USD 15.7, with a NPV increment of 53.52% compared with the base case. The PBP is about 3.55 years after start of operation. The cumulative discounted cash flow for this case is shown in the Figure 4-29. This shown that after paying all the expenses of the project, the revenues of the project will give net value of MM USD 15.7 in the present dollars. For this study case, CODP results in a ROI of 41.8% and a NPV of MM USD 39.17; as shown in numeral 5.3.2.2 a ROI reduction of 3.5% was obtained, but a NPV increment of MM USD 2.7 compared to the base case. The PBP is about 1.19 years assuming as a new plant.

Figure 4-29. Cash flow of MixAlco process in case 1

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4.3.3.2 Case 2. The second case is related to integration between the remaining streams of CODP after heat integration within the plant, and the base case of MixAlco process. Although there was an increased in the capital cost for CODP after its heat integration, there was also a reduction in operation costs around 39%. This was the main reason to make the retrofitting analysis between MixAlco and CODP after heat integration within the CODP plant. Table 4-57. Process streams for case 2
Service H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 Inlet T (C) 130 430 961 500 961 400 266 408 254 165 268 55 55 55 Outlet T MCp (C) (kJ/C-h) 5.61x103 55 2.93x104 -15 5.10x103 130 4.22x103 55 1.67x103 130 2.65x104 130 1.94x104 25 7.02x103 25 2.89x104 43 1.69x105 93 9.83x104 266 8.34x105 47 8.34x105 47 8.33x105 47 Enthalpy Flowrate Name (kJ/h) (kg/h) 4.21x105 6.30x103 PRET-FER.CACO3REC_To_PRET-FER.CACO3 1.31x107 9.59x103 KETONIZA.KET-CACO_To_KETONIZA.KT-CACO3 4.24x106 3.40x102 KETONIZA.H21_To_KETONIZA.H2-1 1.88x106 4.06x103 LIME-KIL.CAO_To_LIME-KIL.CAO-CO2 1.39x106 1.11x102 FINAL.H2-_To_FINAL.H2-1 7.15x106 7.37x103 FINAL.OLF_To_FINAL.OLEFIN 4.68x106 5.28x103 FINAL.HC-C4--8_To_FINAL.LIGHT 2.69x106 2.09x103 FINAL.HC-C9-12_To_FINAL.HEAVY 6.09x106 2.28x104 GASIFICA.C+H2+H20_To_GASIFICA.H2+ 1.22x107 5.00x103 GASIFICA.STEAMSAT_To_GASIFICA.WATER 1.97x105 5.28x103 FINAL. CONDENSER T-101 7.00x106 2.00x105 PRET-FER.SALT3_To_PRET-FER.SALW1 7.01x106 2.00x105 PRET-FER.SALT4_To_PRET-FER.SALW3 7.03x106 2.00x105 PRET-FER.SALT5_To_PRET-FER.SALW5

111

Service H15 H16 H17 H18 H19 H20 H21 H22 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15

Inlet T (C) 50 163 124 188 144 212 60 145 150 150 150 150 150 150 163 -15 130 130 289 55.0 284 97.8 366

Outlet T MCp (C) (kJ/C-h) 8.35x105 42 4.88x106 60 4.17x105 44 8.91x104 75 4.64x105 98 1.14x104 34 6.52x105 49 7.69x104 49 4.51x106 165 4.51x106 165 4.51x106 165 4.51x106 165 4.51x106 165 4.84x106 164 7.86x103 430 2.25x104 130 5.32x104 300 9.61x103 500 4.65x104 408 5.39x106 149.9 5.14x105 381 7.20x104 98.3 3.73x105 432

Enthalpy Flowrate Name (kJ/h) (kg/h) 7.06x106 2.00x105 PRET-FER.H20-FERM_To_PRET-FER.H2O 5.03x108 2.01x105 DEWATER.WATER_To_DEWATER.WATDISTI 4.19x107 6.48x104 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 2.24x107 3.69x104 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 2.16x107 6.48x104 To Condenser@ATM-UNIT.T-204_TO_ATM-UNIT.NAPHT204 2.02x106 5.26x103 VAC-UNIT.LVGOT205_To_VAC-UNIT.LVGO-205 7.24x106 3.00x103 VAC-UNIT.SP-204_heat 7.41x106 3.86x104 UPA_Draw@VAC-UNIT.T-205_To_UPA_Return@VAC-UNIT.T-205 6.83x107 3.34x104 DEWATER.SALWR1_To_DEWATER.SALWR7 6.83x107 3.34x104 DEWATER.SALWR2_To_DEWATER.SALWR8 6.83x107 3.34x104 DEWATER.SALWR3_To_DEWATER.SALWR9 6.83x107 3.34x104 DEWATER.SALWR4_To_DEWATER.SALWR10 6.83x107 3.34x104 DEWATER.SALWR5_To_DEWATER.SALWR11 6.84x107 3.34x104 DEWATER.SALWR6_To_DEWATER.SALWR12 2.10x106 2.52x104 KETONIZA.SAL-DEH_To_KETONIZA.SALT 3.26x106 9.59x103 KETONIZA.KT-CACO3_To_KETONIZA.KET 9.05x106 9.93x103 KETONIZA.ALCOHOL_To_KETONIZA.OH 3.55x106 9.20x103 LIME-KIL.CACO3-2_To_LIME-KIL.CACO3-3 5.53x106 2.09x103 FINAL. REBOILER T-101 5.12x108 2.00x105 DEWATER.SAL-DESC_To_DEWATER.SALT-H20 7.87x107 1.62x105 ATM.UNIT.FURNACE 3.44x104 4.40x103 ATM-UNIT.SP-203_heat 2.48x107 8.88x104 VAC-UNIT.CRDT204_To_VAC-UNIT.CREDT205

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- Heat integration Table 4-57 shows the hot and cold streams of the process available to make the heat integration. Also, it shows the inlet and outlet temperatures, the mass and heat capacity (MCp), the flow rate and the enthalpy of the streams in CODP. The streams to be cooled were 22; meanwhile the streams to be heated were 15. The hot and the cold curves composite are shown in Figure 4-30, where a hot pinch temperature was 155.4C, and cold pinch temperature was 150C. The grand composite curve is shown in Figure 4-31; where the pinch temperature is shown when the net heat flow in the process is zero.

Pinch point

Figure 4-30. Hot and Cold composite for case 2

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Pinch point

Figure 4-31. Grand composite curve for case 2

For MixAlco and CODP, the best heat integration resulted when a Tmin = 5.5C was used. In the heat integration, the hot utilities used were fired heat, MP steam and LP steam. By the other hand, the cooling utilities used were cooling water and refrigerant. The heating and cooling utility load required for the base case was 5.59x108 kJ/h and 2.11x108 kJ/h, respectively. The best heat integration resulted in a heating load of 5.2x108kJ/h and a cooling load of 1.55 x108 kJ/h. It results reduced in 11.21% the operating cost, but increased in 40.25% the capital cost compared with the base case. Table 4-58 summarizes these results.

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Table 4-58. Heat integration for MixAlco and CODP case 2

Base case by joining both plants HEN case 2 (with integration) T (5.5C) 1.10x108 4.07x108 1.50x108 2.79x106 5.38x106 5.20x108 1.55x108 3.21x107 1.13x107

Case 2

Fired Heat (kJ/h) MP Steam (kJ/h) Cooling Water (kJ/h) LP Steam (kJ/h) Refrigerant (kJ/h) Heating (kJ/h) Cooling (kJ/h) Capital cost (USD) Operating cost (USD/year)

1.41x10 4.13x108 1.98x108 4.90x106 1.31x107 5.59x108 2.11x108 2.29x107 1.28x107

Figure 4-32 shows the grid diagram that indicates the configuration of the heat exchangers between the streams in the CODP. Also, it shows the utilities streams for the best arrangement. Table 4-59 to 4-61 show the worksheets of each heat exchangers, heaters and coolers including the temperature of each stream, the area and the heat load. Besides the 24 heat exchanger for CODP integration, are required 15 heat exchangers for the retrofitting analysis, with a total heat load of 6.91x108 kJ/h. The required heaters are 14 for a total heating load of 5.20x108 kJ/h. And, the required coolers are 21 for a total cooling load of 1.55x108 kJ/h.

115

Figure 4-32. Grid diagram for case 2

Table 4-59. Heat exchangers for case 2

Heat Exch Cold Stream Cold T in (C) 62 55 150 Cold T out (C) 148 55 286 Hot Stream GASIFICA.STEAMSAT_To_GASIFICA.W ATER FINAL.OLF_To_FINAL.OLEFIN KETONIZA.KETCACO_To_KETONIZA.KT-CACO3 Hot T in (C) 162 165 290 Hot T out (C) 94 130 168 Load (kJ/h) 1.21x107 9.33x105 3.58x106 Area (m2) 76 3 266

DEWATER.SALE-119 DESC_To_DEWATER.SALT-H20 DEWATER.SALE-166 DESC_To_DEWATER.SALT-H20 KETONIZA.ALCOHOL_To_KETONI E-153 ZA.OH

116

Heat Exch

Cold Stream

Cold T in (C) 62 286 130 51 150 150 150 55 249 62 284 55 183 228 69 44 207 242 228

Cold T out (C) 150 300 150 55 286 165 165 62 254 148 289 62 207 256 96 76 262 257 259

Hot Stream DEWATER.WATER_To_DEWATER.WAT DISTI FINAL.OLF_To_FINAL.OLEFIN 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 FINAL.OLF_To_FINAL.OLEFIN KETONIZA.KETCACO_To_KETONIZA.KT-CACO3 GASIFICA.C+H2+H20_To_GASIFICA.H2+ 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 FINAL.OLF_To_FINAL.OLEFIN 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 KETONIZA.KETCACO_To_KETONIZA.KT-CACO3 To Condenser@ATM-UNIT.T204_TO_ATM-UNIT.NAPHT204 ATM-UNIT.SP-202_heat ATM-UNIT.SP-202_heat MPA_Draw@ATM-UNIT.T204_To_MPA_Return@ATM-UNIT.T-204 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 2-TRAIN.DIEST204_To_2-TRAIN.DISE205 MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 MPA_Draw@VAC-UNIT.T-

Hot T in (C) 162 400 160 173 304 430 254 121 372 188 376 144 250 274 216 188 273 285 275

Hot T out (C) 72 372 173 75 165 376 201 103 304 160 290 98 227 250 148 95 236 275 241

Load (kJ/h) 4.51x108 7.34x105 1.07x106 1.93x107 3.66x106 1.58x106 1.55x106 1.59x107 1.82x10
6

Area (m2) 5,875 4 54 199 149 2 262 153 37 149 139 147 405 1,605 103 132 320 41 600

DEWATER.SALE-120 DESC_To_DEWATER.SALT-H20 KETONIZA.ALCOHOL_To_KETONI E-122 ZA.OH KETONIZA.ALCOHOL_To_KETONI E-155 ZA.OH DEWATER.SALE-157 DESC_To_DEWATER.SALT-H20 KETONIZA.ALCOHOL_To_KETONI E-152 ZA.OH DEWATER.SALWR2_To_DEWATER E-121 .SALWR8 DEWATER.SALWR2_To_DEWATER E-123 .SALWR8 DEWATER.SALE-141 DESC_To_DEWATER.SALT-H20 E-143 ATM.UNIT.FURNACE DEWATER.SALE-124 DESC_To_DEWATER.SALT-H20 E-144 ATM.UNIT.FURNACE DEWATER.SALE-142 DESC_To_DEWATER.SALT-H20 E-148 2-TRAIN.CRDTP1R_ToCRDE207 E-133 ATM.UNIT.FURNACE 1-TRAIN.CRUDE-IN_To_1E-135 TRAIN.CRDTP1 E-149 1-TRAIN.SP-201_heat 2-TRAIN.CRDTP1R_To_2E-126 TRAIN.CRDE207 ATM-UNIT.MPAT204_To_ATME-128 UNIT.MPAM201 E-134 ATM.UNIT.FURNACE

1.19x107 2.53x106 2.08x107 9.73x10 1.06x10

6 7

9.19x106 4.87x106 8.86x106 1.94x106 4.49x10

6

117

Heat Exch

Cold Stream

Cold T in (C)

Cold T out (C)

Hot Stream 205_To_MPA_Return@VAC-UNIT.T-205

Hot T in (C)

Hot T out (C)

Load (kJ/h)

Area (m2)

2-TRAIN.CRDTP1R_To_2E-136 TRAIN.CRDE207 2-TRAIN.CRDTP1R_To_2E-118 TRAIN.CRDE207 ATM-UNIT.MPAT204_To_ATME-140 UNIT.MPAM201 1-TRAIN.CRUDE-IN_To_1E-137 TRAIN.CRDTP1 1-TRAIN.CRUDE-IN_To_1E-139 TRAIN.CRDTP1 2-TRAIN.CRDTP1R_To_2E-129 TRAIN.CRDE207 2-TRAIN.CRDTP1R_To_2E-127 TRAIN.CRDE207 E-131 1-TRAIN.CRUDE-IN_.CRDTP1 2-TRAIN.CRDTP1R_To_2E-125 TRAIN.CRDE207 E-121 2-TRAIN.CRDTP1R_To.CRDE207 1-TRAIN.CRUDE-IN_To_1E-119 TRAIN.CRDTP1 ATM-UNIT.MPAT204_To_ATME-141 UNIT.MPAM201 E-130 ATM.UNIT.FURNACE ATM-UNIT.MPAT204_To_ATME-132 UNIT.MPAM201 2-TRAIN.CRDTP1R_To_2E-124 TRAIN.CRDE207 E-120 2-TRAIN.CRDTP1R_To_CRDE207 E-122 ATM-UNIT.MPAT204_To.MPAM201

206,8

207,1

259 148 31 31 207 207 96

281 230 82 60 232 257 120

2-TRAIN.HVGO_To_2-TRAIN.GPVT205 MPACAL_Draw@ATM-UNIT.T204_To_MPACAL_Return@ATM-UNIT.T204 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 ATM-UNIT.JETT204_To_ATM-UNIT.JETT204 ATM-UNIT.SP-202_heat 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 MPACAL_Draw@VAC-UNIT.T205_To_MPACAL_Return@VAC-UNIT.T205 2-TRAIN.HVGO_To_2-TRAIN.GPVT205 1-TRAIN.DIE203_To_1-TRAIN.DIEST204 MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 2-TRAIN.ASFP205_To_2TRAIN.ASPHALT MPA_Draw@VAC-UNIT.T205_To_MPA_Return@VAC-UNIT.T-205 MPA_Draw@ATM-UNIT.T204_To_MPA_Return@ATM-UNIT.T-204 2-TRAIN.DIEST204_To_2-TRAIN.DISE205 2-TRAIN.HVGO_To_2-TRAIN.GPVT205

251,8

250,7

9.64x104 2.03x106 5.61x106 7.57x106 5.81x106 1.21x106 1.36x106 8.37x10

6

304 251 239 193 277 267 144

288 188 121 68 274 252 124

52 184 74 92 38 52 386

207 259 120 148 257 228 207 259 257

268 277 181 226 283 242 263 275 279

324 324 236 239 390 275 284 289 324

233 268 138 195 285 234 216 273 267

7.87x105 2.03x10
6

15 84 773 133 534 86 473 163 122

2.13x107 5.22x106 1.35x107 1.93x106 9.22x106 3.66x10 3.02x10

6 6

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Table 4-60. Coolers for case 2

Heat Exchanger E-134 E-136 E-168 E-162 E-145 E-147 E-149 E-133 E-169 E-154 E-148 E-150 E-138 E-140 E-164 E-139 E-135 E-137 E-163 E-165 E-146 Utility Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Refrigerant Cooling Water Cooling Water Cooling Water Cooling Water Cooling Water Refrigerant Cooling Water Cooling Water Cooling Water Cooling Water Refrigerant Cooling Water Hot Stream PRET-FER.SALT3_To_PRET-FER.SALW1 FINAL.H2-_To_FINAL.H2-1 FINAL.HC-C4--8_To_FINAL.LIGHT FINAL.HC-C9-12_To_FINAL.HEAVY PRET-FER.SALT4_To_PRET-FER.SALW3 FINAL.CONDENSER T-101 VAC-UNIT.LVGOT205_To_VAC-UNIT.LVGO-205 VAC-UNIT.SP-204_heat KETONIZA.KET-CACO_To_KETONIZA.KT-CACO3 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 PRET-FER.CACO3REC_To_PRET-FER.CACO3 GASIFICA.C+H2+H20_To_GASIFICA.H2+ PRET-FER.H20-FERM_To_PRET-FER.H2O UPA_Draw@VAC-UNIT.T-205_To_UPA_Return@VACUNIT.T-205 KETONIZA.KET-CACO_To_KETONIZA.KT-CACO3 PRET-FER.SALT5_To_PRET-FER.SALW5 1-TRAIN.OVHT204_To_1-TRAIN.OVH202 KETONIZA.H21_To_KETONIZA.H2-1 DEWATER.WATER_To_DEWATER.WATDISTI KETONIZA.KET-CACO_To_KETONIZA.KT-CACO3 LIME-KIL.CAO_To_LIME-KIL.CAO-CO2 Hot T in (C) 55 961 266 408 55 268 213 60 9 103 130 201 50 143 168 55 124 961 72 168 500 Hot T out (C) 46 130 25 25 46 266 34 49 -15 44 55 43 41 49 9 46 121 130 60 9 55 Load (kJ/h) 7.00x106 1.39x106 4.68x106 2.69x106 7.01x106 1.97x105 2.04x106 7.24x106 7.00x105 1.58x107 4.21x105 4.57x106 7.06x106 7.62x106 3.53x106 7.03x106 7.86x106 4.24x106 6.14x107 1.14x106 1.87x106 Area (m2) 35 3 26 12 33 1 17 354 18 128 10 713 44 55 19 35 29 8 181 6 141

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Table 4-61. Heaters for case 2

Heat Exchanger Utility E-132 E-156 E-160 E-131 E-126 E-159 E-161 E-128 E-130 E-125 E-158 E-151 E-127 E-129 MP Steam MP Steam Fired Heat MP Steam MP Steam Fired Heat Fired Heat MP Steam MP Steam Fired Heat Fired Heat LP Steam MP Steam MP Steam Cold Stream DEWATER.SALWR4_To_DEWATER.SALWR10 ATM-UNIT.SP-203_heat VAC-UNIT.CRDT204_To_VAC-UNIT.CREDT205 DEWATER.SALWR3_To_DEWATER.SALWR9 DEWATER.SALWR5_To_DEWATER.SALWR11 LIME-KIL.CACO3-2_To_LIME-KIL.CACO3-3 KETONIZA.SAL-DEH_To_KETONIZA.SALT DEWATER.SALWR1_To_DEWATER.SALWR7 KETONIZA.KT-CACO3_To_KETONIZA.KET ATM.UNIT.FURNACE FINAL.REBOILER T-101 KETONIZA.KT-CACO3_To_KETONIZA.KET DEWATER.SALWR6_To_DEWATER.SALWR12 DEWATER.SALWR2_To_DEWATER.SALWR8 Cold T in (C) 150 98 366 150 150 130 163 150 109 264 289 -15 150 150 Cold T out (C) 165 98 432 165 165 500 430 165 130 381 408 109 164 165 Load (kJ/h) 6.83x107 3.44x104 2.44x107 6.83x107 6.83x107 3.55x106 2.10x106 6.83x107 4.63x105 7.47x107 5.53x106 2.79x106 6.84x107 6.51x107 Area (m2) 297 1 1013 297 297 94 44 297 2 659 191 12 283 284

- Cost analysis The total VOC for MixAlco process with the above integrations resulted in 35,160,509 USD per year, with a reduction of 3.79%, compare with the base case. Table 4-62 shows the VOC for MixAlco process in detail. The total VOC for CODP resulted in 837,612,499 USD per year, with a reduction of 0.11%, compare with the base case. Table 4-63 shows the VOC for CODP in detail.

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Table 4-62. VOC of MixAlco process in case 2 Rate Feedstock Sugarcane baggase Manure Chemical Lime Flocculant Iodoform CaCO3 Utility Fired Heat MP Steam Cooling Water LP Steam Refrigerant Electricity Total VOC 32.0 ton/h 8.0 ton/h 0.900 10.0 3.20 9.00 ton/h kg/h kg/h ton/h Prices 60.0 USD/ton 10.0 USD/ton 70.0 USD/ton 991 USD/ton 25.0 USD/kg 50.0 USD/ton 2.50 USD/ton 4.40 USD/ton 0.00400 USD/m3 4.20 USD/ton 0.0131 USD/ m3 0.0620 USD/kWh Annual cost (USD) 15,360,000 640,000 504,000 79,280 640,000 3,600,000 380,154 7,163,048 185,753 42,483 117,791 6,448,000 35,160,509

18.6 ton/h 205.4 ton/h 5,235.9 m3/h 1.27 ton/h 1,120 m3/h 13.0 MW

Table 4-63. VOC of CODP in case 2 Rate Feedstock Crude oil Utility Fired Heat LP Steam Cooling Water Steam @ 353C Steam @ 454C Electricity Total VOC 162 ton/h 165 0.0160 1,937 4.00 3.00 0.28 ton/h ton/h m3/h ton/h ton/h MW Prices 643 USD/ton 2.50 USD/ton 4.20 USD/ton 0.00400 USD/m3 10.0 USD/ ton 10.0 USD/ ton 0.0620 USD/kWh Annual cost (USD) 833,475,308 3,369,029 546 68,735 320,000 240,000 138,880 837,612,499

The FOC obtained for MixAlco process resulted in 15,429,731 USD per year; with a reduction of 1.08%, compare with the base case. Table 4-64 shows the FOC obtained

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in detail for MixAlco and CODP. The FOC for CODP did not change for the base case, because the operators number and salaries kept equal. Table 4-64. FOC of MixAlco and CODP in case 2 Annual cost (USD) MixAlco CODP Labor Direct wage and benefits (DW&B) Direct salary and benefits Operating supplies and services Technical asistants to manufacturing control laboratory Maintenance Wages and benefits (MW&B) Salaries and benefits Materials and services Maintenance overhead Operating overhead General plant overhead Mechanical department services Employee relations department Business services Total FOC 3,120,000 468,000 187,200 520,000 285,000 3,880,645 970,161 3,880,645 194,032 599,155 202,531 497,890 624,472 15,429,731 2,496,000 374,400 149,760 416,000 228,000 641,529 160,382 641,529 32,076 260,734 88,135 216,666 271,751 5,976,964

The total FCI obtained for MixAlco process was USD 110,875,569; in this value capital cost saving for mass and heat integration was discount; resulting in a reduction of 1.67% compared with the base case. The WCI was USD 11,087,557, and the TCI results in USD 121,963,125. The total FCI for CODP is USD 15,251,392, because an investment is required for the new heat equipment arrangement. In CODP possible revenue from selling heat equipment to be replaced, was no accounted.

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Table 4-65 shows the obtained profitability results for MixAlco process and CODP, with and without the time value of money applying the integration mentioned in this numeral. Table 4-65. Summary MixAlco and CODP economic results in case 2
MixAlco with integration Value CODP with integration Value

Parameter

Profitability without the time value of money ROI estimated (%) 16.4 22,287,333 Annual gross (pre tax) profit (USD) 18,184,937 Annual net (after tax) profit (USD) PBP (years) 3.56 Total operating cost (USD) 50,590,241 FCI (USD) 110,875,569 WCI (USD) 11,087,557 TCI (USD) 121,963,125 Profitability with the time value of money 15,288,147 12.35 72,877,573 35 10

66,21 10,661,731 10,097,429 1.28 843,589,462 15,251,392 1,525,139 16,776,531

NPV (USD) ROI real (%) Annual sales (USD) Tax rate (%) Discount rate (%)

35,568,846 39.04 854,251,193 35 10

The retrofitting analysis in case 2 for MixAlco process results in a ROI of 12.35% acceptable in current market conditions; a ROI increment in 1.3% compared with the base case. The NPV represent a profitable project of MM USD 15.3, with a NPV increment of 52.27% compared with the base case. The PBP is about 3.56 years after start of operation. The cumulative discounted cash flow for this case is shown in the Figure 4-33. This shown that after paying all the expenses

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of the project, the revenues of the project will give net value of MM USD 15.3 in the present dollars. For this study case, CODP results in a ROI of 39% and a NPV of MM USD 35.6. To compare the convenience of the retrofitting analysis in CODP, the profitability of CODP integrated as a new plant was evaluated, as in the base case. The results show that CODP integration had a reduction of ROI in 5.3%, and a NPV reduction in MM USD 0.80 was obtained compared to the base case. The PBP for CODP is about 1.28 years assuming as a new plant.

Figure 4-33. Cash flow of MixAlco process in case 2

4.3.3.3 Comparison between cases Table 4-66 shows the heat integration comparing the cases 1 and 2. For both cases, the processes (MixAlco and CODP) presented arrangements with operating cost savings.

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Although in both cases there was a capital investment, the global economic evaluation presented revenues. Table 4-66. Heat integration comparison of cases
Base case by joining both plants Fired Heat (kJ/h) MP Steam (kJ/h) Cooling Water (kJ/h) LP Steam (kJ/h) Refrigerant (kJ/h) Heating (kJ/h) Cooling (kJ/h) Capital cost (USD) Operating cost (USD/year) 1.41x108 4.13x108 1.98x108 4.90x10 1.31x10 5.59x10 2.11x10 2.29x10 1.28x10
6 7 8 8 7 7

% % % Difference Case 1 Case 2 Difference Difference between case 1 case 2 cases 8.25x107 1.10x108 71.0 % 28.0 % 25.0 % 8 8 4.08x10 4.07x10 1.00 % 1.00 % 0% 1.44x108 1.50x108 38.0 % 2.73x106 2.79x106 79.0 % 1.10x10 5.38x10 4.94x10 5.20x10 1.45x10 1.55x10 2.83x10 3.21x10
7 8 8 6 6 8 8 7

32.0 % 76.0 % 143% 8.00 % 36.0 % 29.0 % 13.0 %

4.00 % 2.00 % 80.0 % 5.00 % 6.00 % 12.0 % 9.0 %

1.09 % 13.0 % 46.0 %

19.0 % 1.03x107 1.13x107 24.0 %

Table 4-67 shows the NPV and ROI for both retrofitting cases. For MixAlco process the ROI obtained in both cases is almost the same, but the NPV in case 1 is 2.6% higher than in case 2. For CODP the ROI in case 1 is higher 2.8% than case 2, and the NPV is 10% higher in case 1 than in case 2. Based on these results, it is possible to affirm that case 1 is economically more profitable than case 2 for MixAlco process and even more for CODP. Table 4-679. Economic comparison of cases Case 1 MixAlco CODP 15.7 39.2 12.4 41.8 Case 2 MixAlco CODP 15.3 35.6 12.3 39.0

NPV (MM USD) ROI (%)

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4.4 Sensitivity analysis In this section, different variables were modified in order to study the behavior of the ROI in each option. The understanding of the sensitivity analysis of the ROI helps in making the optimal decision under given conditions. 4.4.1 Variation of gasoline prices The first sensitivity analysis was based on the gasoline prices performance between years 2010 to 2013 shown in Figure E-8 (Appendix E). The prices of gasoline were changed from 2.5 to 3.8 USD per gallon.

Figure 4-34. Variation of gasoline price for MixAlco process

For the best case of retrofitting and the base case, Figure 4-34 shows the result of ROI and NPV of MixAlco process for different gasoline prices. With limited ROI (5%) the minimum selling price of gasoline is 2.7 USD per gallon. With a gasoline price of 3.8

126

USD per gallon the ROI obtained was 18%. From the NPV analysis, MixAlco process starts to be not profitable with gasoline price below 3.07 USD per gallon. 4.4.2 Variation of Jet prices The second sensitivity analysis was based on the Jet prices performance between years 2010 to 2013 shown in Figure E-7 (Appendix E). The prices of Jet were changed from 2 to 3.8 USD per gallon.

Figure 4-35. Variaton of Jet price for MixAlco process

For the best case of retrofitting and the base case, Figure 4-35 shows the result of ROI and NPV of MixAlco process for different Jet prices. Where, ROI does not reach the minimum limit (5%). With a Jet price of 3.8 USD per gallon the ROI obtained was 15.8%. From the NPV analysis, MixAlco process starts to not be profitable with Jet price below 2.3 USD per gallon.

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4.4.3 Variation of Biomass price Based on the Pham et al., (2012) study, the price of biomass feedstock could be changed from 20 to 120 USD per ton. Figure 4-36 shows the variation of Biomass prices from 0 to 120 USD per ton. When the price of biomass is free, the ROI is 21.5%, maintaining the MixAlco plant capacity of 60 ton/h. Also, Figure 4-36 shows the

maximum price of Biomass in 73 USD/ton in order to have the NPV positive and the project will be profitable.

Figure 4-36. Variation of Biomass price

4.4.4 Variation of MixAlco plant capacity The fourth sensitivity analysis was based on the MixAlco plant capacity, varying the biomass feedstock from 20 to 160 ton/h. To do that, the FCI was calculated using the six tenths factor rule explained in Appendix E, with a scaling factor of 0.6, according to the

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literature (Pham et al., 2010). The consumption of utilities and chemicals had been calculated, and the annual sales should be adjusted for each capacity. In this analysis the biomass price was constant in 60 USD/ton. For the best retrofitting case, Figure 4-37 shows the result of ROI and NPV varying the MixAlco plant capacity. From the NPV analysis, MixAlco process starts to be profitable with an approximated 33 ton/ h of capacity. With a MixAlco plant capacity above 70ton/h was provided a ROI higher than 20%.

Figure 4-37. Variation of MixAlco plant capacity

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CONCLUSIONS

In order to evaluate the retrofitting analysis to integrate the MixAlco process to the crude oil distillation process (CODP), this work was developed in four stages. The first stage was the building of each process (as a base case) with mass and energy balances and economical evaluation. In this way, a simulation of the entire MixAlco process was made. This simulation used a feedstock stream (sugarcane bagasse/chicken manure) of 40ton/h, using ketonization process route. The results obtained for MixAlco simulations were the expected, according to literature (Pham et al., 2012), (Gosseaume, 2011), (Holtzapple, 2004), (Pham, Holtzapple, & El-Halwagi, 2012). Also, a typical crude oil distillation process for commercial crude oil with 22.4API was simulated with preheating trains and atmospheric/vacuum units. In the second stage, the hierarchical methodology proposed was used as a strategy to achieve cost-effective studies through profitability analysis. Different levels for applying the hierarchical methodology were done: - Internal rearrangements within each process, where it was obtained only a mass integration within MixAlco process. Considering, recycle water from dewatering unit to fermentation and pretreatment units. The base case of MixAlco was obtained with a ROI of 11.1% and a NPV of MM USD 7.3. The base case of CODP was obtained with a ROI of 31.2% and a NPV of MM USD 29 as a new plant. - Internal modifications within each process, where heat integration within each plant was made. For MixAlco the heating and cooling utility load, results reduced in 8.3% the capital cost and in 8.6% the operating cost. Also, it was obtained a ROI of 11.8% and a NPV of MM USD 11.7. For CODP the heating and cooling utility load, reduced in 39%

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the operating cost but increased a capital cost 78%. In this case CODP obtained a ROI of 41.8% and a NPV of MM USD 39.2. - External modification through retrofitting analysis between MixAlco process and CODP, where two relevant cases where analyzed and compared. The first case was based on a mass and heat integration within each process. Also, water integration between both plants was made. The economical results were a 12.4% of ROI, and MM USD 15.7 of NPV for MixAlco process. The second case was based on integration of both plants, where MixAlco process was added to CODP with heat integration inside the plant. Results presented a ROI of 12.35% and NPV of MM USD 15.3 for MixAlco process. The third stage was the comparison between the two cases mentioned above, where the case 1 resulted in the best retrofitting analysis. There was an NPV increment from MM USD 7.3 to MM USD 15.7, and ROI increment from 11.1% to 12.4% for MixAlco process. According to retrofitting results, it is necessary to make an investment in capital cost of MM USD 15 for CODP that will be payback in 15 months (according to profitability analysis). The fourth stage was a sensitivity analysis to MixAlco process for the best retrofitting case. The mainly results for MixAlco be profitable were a minimum gasoline price of 3.07 USD per gallon, and a minimum Jet price of 2.3 USD per gallon. Besides, with the maximum price of gasoline or Jet (3.8 USD per gallon) an obtained ROI was 18% and 15.8% respectively. For a MixAlco plant capacity of 60 ton/h was obtained a ROI of 21.5% if the biomass price was free; and the maximum price of biomass was 73 USD/ton in order to have the NPV positive and the project will be profitable. Finally, MixAlco

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process starts to be profitable from about 33 ton/ h of capacity. For a MixAlco capacity above 70ton/h was obtained ROIs above 20%.

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6. RECOMMENDATIONS AND FUTURE WORK After completing this work, it is considered important to research in future works into the optimization of the mixture of both products (bio-gasoline / gasoline), in order to optimize the retrofitting analysis. It is considered important to study in future works the plant capacity of MixAlco and CODP, getting a better compatibility in the Pinch point. It is recommended to study a case of both plants (MixAlco and CODP) as news, different that was done in this work, and compare the cases. In order to verify the MixAlco process simulation is recommended validate it with Terrabon, the demostration plant of MixAlco located in College Station, Texas. It is recommended to study in future works different ways of heat integration, for example study the integration of syngas from MixAlco with the furnace located in the atmospheric unit of CODP. Moreover, study other types of heat exchangers as compact heat exchangers. Otherwise, include the fouling affectation in the preheating system with the time. It is also considered important to include in future works, the study of life cycle analysis (LCA) into a bio-refinery retrofitting analysis, in order to evaluate the greenhouse gas emissions (GHG) and associate it with the economic evaluation by Clean Development Mechanism (CDM). Furthermore, it is recommended to investigate the retrofitting analysis on other products, in order to integrated biofuels into the existing fossil-based process.

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Finally, it is recommended to develop a computational template which integrates all calculations of integration, technical and economic analysis and the selection of the best alternative.

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REFERENCES Aspen plus. (2013). Software database and help menu (Version 7.3). Benali, T., & Tondeur, J. N. (2011). An improved crude oil atmospheric distillation process for energy integration: Part I: Energy and exergy analyses of the process when a flash is installed in the preheating train. Applied Thermal Engineering. 125 -131. Cormier, B. (2005). Retrofitting Analysis of Integrated Bio-refineries. Texas A&M University, College Station, TX. EIA. (2013, July 9). Retrieved 2013, 13-July from the U.S. Energy Information Administration: http://www.eia.gov/forecasts/steo/report/global_oil.cfm EIA. (2013, July 15). Retrieved 2013, 10-June from the U.S. Energy Information Administration: http://www.eia.gov/dnav/pet/hist/LeafHandler.ashx?n=PET&s= EMM_EPMRU_PTE_R30_DPG&f=W El-Halwagi, M. (2012). Sustainable design through process integration. Texas: Elsevier. El-Halwagi, M., & Spriggs, H. D. (1998). Solve Design Puzzles with Mass Integration. Chemical engineering progress, 8(94), 25-44. Felder, R., & Rousseau, R. (2005). Elementary principles of chemical processes. Atlanta: John Wiley & Sons, Inc. Fernndez, J. (2007). Diseo de un modelo de optimizacin de la planta de crudo de Ecopetrol S.A. en la Refinera de Cartagena. Magister thesis in Industrial Engineering. Bogot.

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Gosseaume, P. (2011). Development of a simulation tool of the MixAlco Technology to be applied in Colombia. Grenoble INP-Pagora, France. Granda, C., Holtzapple, M., Luce, G., Searcy, K., & Mamrosh, D. (2009). Carboxylate Platform: The MixAlco Process Part 2: Process Economics. Appl Biochem Biotechnol, 537 - 554. Holtzapple, M. (2004). MixAlco Process: Biomass to Carboxylic Acids and Alcohols. College Station, TX. Holtzapple, M. (2009). Patent application 'Methods and Systems for Biomass Conversion to Carboxylic Acids and Alcohols'. Peters, M., Timmerhaus, K., & West, R. (2004). Plant Design and Economics for Chemical Engineers. 5th Edition. Colorado: Mc Graw Hill. Pham, V., Holtzapple, M., & El-Halwagi, M. (2010). Techo-economic analysis of biomass to fuel conversion via the MixAlco process. J Ind Microbiol Biotechnol. Pham, V., Holtzapple, M., & El-Halwagi, M. (2012). Chapter 6. Technoeconomic Analysis of a Lignocellulose-to-Hydrocarbons Process Using a Carboxylate Platform. Integrated Biorefineries: Design, Analysis, and Optimization (Green Chemistry and Chemical Engineering) (p. 157 - 192). Texas. Chapman & Hall. Seider, W., Seader, J. D., & Lewin, D. (2004). Product & Process Design Principles. 2nd Edition. Wiley.

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Sierra, R., Garca, L., & Holtzapple, M. (2010). Selectivity and Delignification Kinetics for Oxidative and Nonoxidative Lime Pretreatment of Poplar Wood, Part III: LongTerm. AIChE. Terrabon. (2010, October). Retrieved 2010, 12-October from:

http://www.terrabon.com/mixalco_economics.html Towler, G., & Sinnott, R. (2013). Chapter 7. Capital Cost Estimating. Chemical Engineering Design (pgs. 307 - 351). Elsevier. Wooley, R., & Putsche, V. (1996). Development of an Aspen Plus Physical Property Database for Biofuels Components. Golden, Colorado. Zhihong, F., & Holtzapple, M. (2010). Fermentation of Sugarcane Bagasse and Chicken Manure to Calcium Carboxylate under Thermophilic Conditions. Appl Biocehm Biotechnol, 561-578.

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APPENDIX A A.1 Literature review A.1.2 MixAlco Process Description The MixAlco process is a robust process that converts biomass to fuels and chemicals. A key feature of the MixAlco process is the fermentation, which employs a mixed culture of acid-forming microorganisms to convert biomass components (carbohydrates, proteins, and fats) to carboxylate salts. Subsequently, these intermediate salts are chemical converted to hydrocarbon fuels (gasoline, jet fuel, and diesel). (Pham et al., 2010) Figure A-1 shows biomass-to-hydrocarbon fuels conversion via ketonization. To make hydrocarbon fuels, the MixAlco process uses the following steps: (I) pretreatment with lime, (II) fermentation with a mixed culture of acid-forming microorganism to obtain carboxylate salts, (III) dewatering using a high-efficiency vapor-compression evaporator, (IV) thermal conversion of salts to ketones (V) hydrogenation of the ketones to mixed alcohols, and (VI) oligomerization of alcohols to hydrocarbons using zeolite catalysts. (Pham et al., 2010)

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Figure A-1. MixAlco process via Ketonization. (Pham et al., 2010)

The biomass feedstock must contain a source of energy and a source of nutrients. Examples of energy sources include sorghum, bagasse, municipal solid waste, office paper, paper fines, rice straw, water hyacinths, pineapple waste, and aloe-vera pulp. Examples of nutrient sources include food scraps, sewage sludge, and manure. In addition, chemical nutrients (e.g., urea, ammonia, ammonium bicarbonate) can be added to supply essential minerals. (Pham et al., 2010)

FEED HANDLING Figure A-2 shows a schematic of the loading facilities. Screw conveyor A-2 augers quick lime (CaO) into mixer A-3, which blends biomass, quick lime, water, and calcium carbonate. The quick lime reacts with water, releasing heat which raises the temperature of the mixture. The biomass/lime/water/calcium carbonate mixture is fed to loader A-1, which stores a few hundred tons of the mixture. (Holtzapple, 2004)

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Figure A-2. Schematic of loading facilities. (Holtzapple, 2004)

PRETREATMENT AND FERMENTATION Different forms of pretreatment exist, using physical, chemical or biological means. It has been found hat pretreatment with lime and air efficiently delignifies lignocellulosic materials, increasing digestibility significantly. This type of pretreatment is preferred over other pretreatment options for the MixAlco process because it is best integrated with further processing and recovery steps. (Gosseaume, Development of a simulation tool of the MixAlco Technology to be applied in Colombia, 2011)

Recycled lime from the lime kiln is assumed to contribute 85% of lime demand in the pretreatment, with the 15% make-up lime purchased from external vendors. Although the residence time of pretreatment (6 weeks) and fermentation (8 weeks) is long, the roundrobin system results in steady flow rate and product concentration in the broth. (Pham et al., 2010)

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An example of the pretreatment/fermentation piles operated in a round-robin manner is presented in figure A3, where there are six piles, two pretreatment and four in fermentation. As the lime pretreatment pile ages, the pH drops. Then the air is shut off, and the inoculum is added, so it becomes a fermentation pile. When the fermentation is complete, the residue is removed, and pretreatment starts with a new pile. Figure A4 shows the water circulation pattern while in the fermentation mode. (Granda, Holtzapple, Luce, Searcy, & Mamrosh, 2009)

Figure A-3. Round - robin system. (Granda et al., 2009)

Freshest biomass

Most digested biomass

Figure A-4. Water circulation through the piles. (Granda et al., 2009)

Figure A-5 shows the pile in the pretreatment mode. A blower (A-5) pressures air and blows it through a lime-water slurry tank (A-6), which removes carbon dioxide from the air. The air then blows up through the pile, which contains both biomass and lime. The

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pile is located on a gravel bed lined with a geomembrane. Water accumulates in the gravel bed and is circulated to the top of the pile. The combination of lime, water, and air removes lignin from the biomass, rendering it digestible. During the pretreatment mode, the pile can be covered or uncovered. If covered, an exhaust blower (A-7) removes gas from the pile. A slight vacuum can be created, which keeps the cover pressed against the pile thereby keeping it from blowing in the wind. Liquid collected from the bottom of the pile is pumped (A-8) through a heat exchanger (A-9) onto the top of the pile. (Granda et al., 2009)

Figure A-5. Pretreatment pile. (Granda et al., 2009) Once the lime is consumed within the pile, the pH will drop. At this point, the pile is inoculated with a mixed culture of acid-forming microorganisms that digest the biomass and form volatile fatty acids (VFAs) such as acetic, propionic, and butyric acids. The VFAs react with the calcium carbonate within the pile, thus forming salts of the VFAs, such as

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calcium acetate, propionate, and butyrate. Because they tolerate high salt concentrations, the best source of the inoculum is from saline environments. (Holtzapple, 2004)

Holtzapple, (2004) show in Figure A-6 the pile in the fermentation mode. In this case, no air circulates through the pile and the exhaust gases are sent to a packed bed scrubber (A-10) where they contact ammonia and water to form ammonium bicarbonate buffer for our case the buffer is calcium carbonate, which is stored in a holding tank (A-11) and directed to the liquid that circulates through the pile. Gases exiting the scrubber (A-10) are sent to an odor control system (A-12) if no hydrogen is present in the gas. If hydrogen is present, then the gas is sent to a hydrogen recovery unit (not shown).

Figure A-6. Pile in Fermentation form. (Granada et al., 2009)

Figure A-7 shows that after the fermentation is completed, the pile is dismantled by slurrying the undigested residue with water (A-14) and pumping (A-13) the slurry through

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a filter (A-16). The undigested residue can be sent to a boiler to make process heat, a gasifier to make hydrogen, or it can be exported for other purposes (compost, electricity production). (Granada et al., 2009)

Figure A-7. Dismantling the fermentation pile. (Granada et al., 2009)

Biomass is composed of volatile solids (VS) and ash. Most of the VS are reactive except lignin, whereas the ash content is nonreactive. Mass balances closure is performed during steady-state countercurrent fermentations. Figure A-8 illustrates a typical fermentation process, which converts VS into gas and liquid products, with some solids remaining undigested. (Zhihong & Holtzapple, 2010).

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Figure A-8. Digestion of biomass. (Zhihong & Holtzapple, 2009)

DESCUMMING AND DEWATERING In the produced fermentation broth, the calcium carboxylate concentration is 6% weight. Other components (e.g., dissolved carbon dioxide, microorganisms, undigested biomass, and other unknowns) are impurities and must be removed along with water. To purify the carboxylate salts, the broth is degasified by stripping, descummed using flocculant, evaporated using vapor compression, and crystallized (Figure A-9). (Pham et al., 2010)

Figure A-9. Simplified process block of the descumming and dewatering units. (Pham et al., 2010)

KETONIZATION AND LIME KILN The solid salts are sent to a dryer to remove residual moisture (Figure A-10). At high temperatures (430C) in the ketonization reactor, calcium carboxylates are thermally

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converted into ketones and calcium carbonate. The reactor is kept under vacuum (30 mmHg), which reduces residence time to avoid decomposition of the produced ketones. The ketone vapor is quickly removed from the reactor, quenched, and condensed. (Pham et al., 2010)

Figure A-10. Simplified process block of the ketonization and lime kiln unit. (Pham et al., 2010) The general ketonization reaction is represented as following:

Carboxylate calcium

Ketone

Calcium carbonate

Part of the calcium carbonate is directly recycled to the fermentors, and the remaining portion is converted into quick lime (CaO) in a kiln. The quick lime is recycled to the pretreatment reactors. Unlike conventional lime kilns that are fed coarse limestone, this kiln processes fine calcium carbonate powder; thus, some processing steps (grinding, drying) are not needed. This reaction takes place at 900C or 1000C. (Pham et al., 2010)

KETONE HYDROGENATION In this conversion step, the ketone carbonyl groups react with hydrogen to form alcohol groups in an exothermic reaction:

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Ketone

Hydrogen

Alcohol

The reaction is performed at high pressure (55 bar) and at isothermal (130C) condition. The optimal design was found to be three continually stirred tank reactors (CSTR) in series. In each CSTR, liquid ketones, solid Raney nickel catalyst, and hydrogen bubbles are well mixed. The heat of reaction is recovered by a pump-around system. Hydrogen is fed to every CSTR in 20%excess to maximize ketone conversion. The net demand of hydrogen is 0.0225 kg H2/kg mixed alcohol [25.0 standard cubic foot (SCF) per gallon of mixed alcohols] or 0.00687 kg H2/kg dry ash-free biomass (1.30 SCF per dry ashfree pound of biomass). The produced mixture of secondary alcohols can be directly used as a transportation oxygenated fuel such as bioethanol, but it has higher energy content (net heating values are 34.6 and 26.8 MJ/kg, respectively. (Pham et al., 2010)

DEHYDRATATION AND OLIGOMERIZATION The mixed alcohols are further processed to produce hydrocarbon fuels. Using HZSM-5 catalyst in a reactor at 300C and 3 bar, the alcohols are dehydrated as follows:

Alcohol

Olefins

Water

In the same reactor, the produced olefins are oligomerized as shown in the following simplified reaction:

Olefins

Longer Olefins

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Depending upon the specific reaction conditions (time, pressure, temperature) the products are very complex and include olefins, n-paraffins, iso-paraffins, aromatics, and cyclics. Water in the products is removed in a drying unit using a salt filter. (Pham et al., 2010)

OLEFIN HYDROGENATION To improve fuel quality, the olefins can be hydrogenated to make corresponding paraffins. Similar to the design of the ketone hydrogenation, this conversion unit employs CSTRs in series with Raney nickel catalyst. The carbon double bond (C=C) is saturated to stabilize the hydrocarbon product as follows:

Olefins

Paraffins

In this step, the net demand of hydrogen is 0.0139 kg H2/kg hydrocarbon fuels (15.4 SCF per gallon of hydrocarbon fuel) or 0.0034 kg H2/kg dry ash-free biomass (0.64 SCF per dry ash-free pound of biomass). (Pham et al., 2010)

Out of the reactor, the mixed hydrocarbons are distilled into C8- and C9+ fractions. The light fraction and heavy components can be used as blending components for gasoline and jet fuel, respectively. (Pham et al., 2010)

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GASIFICATION Hydrogen is required to produce alcohols and saturate hydrocarbons. This hydrogen is produced by gasifying undigested biomass from the fermenters. (Pham et al., 2010)

STEAM-GAS SHIFT AND PRESSURE-SWING ADSORPTION More hydrogen is made using the shift reaction between steam and carbon monoxide. Because of the compositional characteristics of the syngas, a one-stage shift is sufficient for high conversion and low residence time. The hydrogen-rich syngas, along with fermentation gas, is passed through molecular sieve beds in the pressure-swing adsorption unit, which purifies hydrogen. (Pham et al., 2010) A.2 Consideration in MixAlco Process Simulation A.2.1 Fermentation Biomass to Sugar (Eq. A-1) Cellulose Glucose (Eq. A-2) Xylan Sugar to Acid (Eq. A-3) Glucose Acid acetic (Eq. A-4) Glucose Acid propionic (Eq. A-5) Glucose Acid valeric (Eq. A-6) Xylose Acid acetic Xylose

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(Eq. A-7) Xylose Acid propionic (Eq. A-8) Xylose Acid neutralization (Eq. A-9) Acid acetic Calcium acetate (Eq. A-10) Acid propionic Calcium propionate (Eq. A11) Acid valeric Calcium pentanoate Acid valeric

Table A-1. Conversion factors in fermentation reactors Reactions 1 CELLU-01(Cisolid) + WATER --> GLUCO-01 2 XYLAN(Cisolid) + WATER --> XYLOS-01 3 GLUCO-01 --> 3 A-ACETI 4 GLUCO-01 --> 2 A-PROP + .727 CO2 5 5 GLUCO-01 --> 6 A-VAL + 6.543 CO2 6 2 XYLOS-01 --> 5 A-ACETI 7 3 XYLOS-01 --> 5 A-PROP + 1.818 CO2 8 XYLOS-01 --> A-VAL + 1.09 CO2 9 2 A-ACETI + CACO3(Cisolid) --> WATER + CO2 + CA(CH-01(Cisolid) 10 2 A-PROP + CACO3(Cisolid) --> CA(CH02(Cisolid) + WATER + CO2 11 2 A-VAL + CACO3(Cisolid) --> CA(CH03(Cisolid) + WATER + CO2 R-102 0.3823 0.3823 0.840 0.0500 1.00 0.800 0.250 1.00 1.00 1.00 1.00 R-103 0.4741 0.4741 0.840 0.0500 1.00 0.800 0.250 1.00 1.00 1.00 1.00 R-104 0.517 0.517 0.840 0.0500 1.00 0.800 0.250 1.00 1.00 1.00 1.00 R-105 0.542 0.542 0.840 0.0500 1.00 0.800 0.250 1.00 1.00 1.00 1.00

A.2.2 Ketonization

Carboxylate salts to ketone (Eq. A-12) Calcium acetate Acetone

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Calcium acetate

Calcium propionate

(Eq. A-13) Butanone (or Methyl-ethyl ketone)

(Eq. A14)

Calcium acetate

Calcium pentanoate

2-hexanone (or methyl buthyl ketone) (Eq. A-14)

Calcium propionate

3-pentanone
(Eq.A15)

Calcium propionate Calcium pentanoate

3-heptanone (Eq. A-16)

Calcium pentanoate Ketone to Alcohol

5-nonanone

(Eq. A-17) Acetone Isopropanol (Eq. A-18) Butanone Sec-butanol (or 2-butanol) (Eq. A-19) 2-hexanone 2- hexanol (Eq. A-20) 3-pentanone 3- pentanol (Eq. A-21) 3-heptanone 3- heptanol
(Eq.A22)

5-nonanone

5-nonanol

A.2.3 FINAL Dehydratation (Eq. A-23) Isopropanol C3H6 = Propylene (Eq. A-24) 2-butanol C4H8 = 2-butene

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(Eq. A-25) 2- hexanol C6H12 = 2-hexene (Eq. A-26) 3- pentanol C5H10= 2-pentene (Eq. A-27) 3- heptanol C7H14 = 1,2-dimethylcyclopentane (Eq. A-28) 5-nonanol Oligomerization (Eq. A-29) Propylene + 2-butene 1,2-dimethylcyclopentane (Eq. A30) 1,2-dimethylcyclohexane (Eq. A31) 2-nonene (Eq. A-32) 1,4-diethylcyclohexane (Eq. A-33) undecene (Eq. A-34) 1-dodecene (Eq. A-35) 2-nonene (Eq. A-36) Propylene+ Propylene 2-hexene C9H18 = 2-nonene

Propylene +2-pentene

Propylene +2-hexene

Propylene + 1,2-dimethylcyclopentane

Propylene + 1,2-dimethylcyclohexane

Propylene + 2-nonene

2-butene + 2-pentene

Olefin hydrogenation (Eq. A-37) 2-butene butane

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(Eq. A-38) 2-pentene pentane (Eq. A-39) 2-hexene hexane (Eq. A-40) 1,2-dimethylcyclopentane heptane (Eq. A-41) 1,2-dimethylcyclohexane octane (Eq. A-42) 2-nonene nonane (Eq. A-43) 1,4-diethylcyclohexane decane (Eq. A-44) undecene undecane (Eq. A-45) 1-dodecene dodecane

Table A-2. Conversion factor for reactor R-111 Oligomerization Conversion C3H6 + C4H8 --> C7H14 0.2 C3H6 + C5H10 --> C8H16 0.4 C3H6 + C6H12 --> C9H18 0.7 C3H6 + C8H16 --> C11H22 0.2 C3H6 + C9H18 --> C12H24 0.2 C4H8 + C5H10 --> C9H18 0.4 C5H10 + C6H12 --> C11H22 0.95 2 C3H6 --> C6H12 0.5

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APPENDIX B Table B-1. Components List in MixAlco simulation (Gosseaume, 2011)

Component ID CELLU-01 XYLAN LIGNI-01 BIOMA-01 GLUCO-01 XYLOS-01 SOLSL-01 SOLUN-01 WATER AIR CO CO2 CA(OH)2 CACO3 CA(CH-01 CA(CH-02 CA(CH-03 NITROGEN O2 CAO A-ACETI A-PROP A-VAL HYDROGEN ACETONE BUTANONE HEXANONE PENTANON HEPTANON NONANONE ISOPROPA BUTANOL HEXANOL PENTANOL HEPTANOL NONANOL 1-BUT-01 C3H6 C4H8 C5H10 C6H12 C7H14 C9H18 Type SOLID SOLID SOLID SOLID CONV CONV CONV CONV CONV CONV CONV CONV SOLID SOLID SOLID SOLID SOLID CONV CONV SOLID CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV Component name CELLULOSE XYLAN LIGNIN BIOMASS GLUCOSE XYLOSE SOLSLDS SOLUNKN WATER AIR CARBON-MONOXIDE CARBON-DIOXIDE CALCIUM-HYDROXIDE CALCIUM-CARBONATE-CALCITE CA(CH3CO2)2 CA(CH3CH2CO2)2 CA(CH3CH2CH2CH2CO2)2 NITROGEN OXYGEN CALCIUM-OXIDE ACETIC-ACID PROPIONIC-ACID N-VALERIC-ACID HYDROGEN ACETONE METHYL-ETHYL-KETONE 2-HEXANONE DIETHYL-KETONE 3-HEPTANONE 5-NONANONE ISOPROPYL-ALCOHOL 2-BUTANOL 2-HEXANOL 3-PENTANOL 3-HEPTANOL 1-NONANOL 1-BUTENE PROPYLENE CIS-2-BUTENE TRANS-2-PENTENE TRANS-2-HEXENE TRANS-1,2-DIMETHYLCYCLOPENTANE TRANS-2-NONENE Formula C6H10O5 C5H8O4 CXHXOX CHXNXOXSX-1 C6H12O6 C5H10O5 CHXOXSX CXHOX H2O AIR CO CO2 CA(OH)2 CACO3 CAC4H6O4 CA(PROP)2 CA(PENT)2 N2 O2 CAO C2H4O2-1 C3H6O2-1 C5H10O2-1 H2 C3H6O-1 C4H8O-3 C6H12O-D3 C5H10O-4 C7H14O-E1 C9H18O-E2 C3H8O-2 C4H10O-2 C6H14O-E1 C5H12O-D4 C7H16O-D4 C9H20O-D2 C4H8-1 C3H6-2 C4H8-2 C5H10-4 C6H12-5 C7H14-4 C9H18-D5

154 Component ID C8H16 C10H20 C11H22 C12H24 C13H26 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C11H24 C12H26 C13H28 C12H24 C13H26 Type CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV CONV Component name TRANS-1,2-DIMETHYLCYCLOHEXANE TRANS-1,4-DIETHYLCYCLOHEXANE 1-UNDECENE 1-DODECENE 1-TRIDECENE N-BUTANE N-PENTANE N-HEXANE N-HEPTANE N-OCTANE N-NONANE N-DECANE N-UNDECANE N-DODECANE N-TRIDECANE 1-DODECENE 1-TRIDECENE Formula C8H16-3 C10H20-D7 C11H22-2 C12H24-2 C13H26-2 C4H10-1 C5H12-1 C6H14-1 C7H16-1 C8H18-1 C9H20-1 C10H22-1 C11H24 C12H26 C13H28 C12H24-2 C13H26-2

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Table B2. Components properties for MixAlco process. (Aspen plus, 2013)
TBP (C) 215.9 322.4 343.9 100.0 -194.5 -191.5 -78.5 -195.8 -183.0 117.9 141.2 185.8 -252.8 56.3 79.6 127.6 102.0 147.4 188.5 82.2 99.8 139.3 115.3 156.0 212.1 -6.2 -47.7 3.7 36.3 67.9 91.9 150.1 123.4 176.3 192.7 213.0 232.8 VLSTD (cm3/mol) 147.0 103.5 152.6 18.1 32.9 53.6 53.6 53.6 53.6 57.6 74.3 108.4 53.6 74.0 89.3 124.1 106.4 140.3 174.0 76.3 91.6 126.1 107.9 141.6 175.0 93.6 80.9 89.7 107.6 123.6 130.2 173.0 144.2 176.2 205.0 221.3 237.6

COMPONENT API DHFORM (kJ/mol) CELLU-01 XYLAN GLUCO-01 WATER AIR CO CO2 NITROGEN O2 A-ACETI A-PROP A-VAL HYDROGEN ACETONE BUTANONE HEXANONE PENTANON HEPTANON NONANONE ISOPROPA BUTANOL HEXANOL PENTANOL HEPTANOL NONANOL 1-BUT-01 C3H6 C4H8 C5H10 C6H12 C7H14 C9H18 C8H16 C10H20 C11H22 C12H24 C13H26 -3.6 -20.9 -11.9 10.0 28.9 340.0 340.0 340.0 340.0 2.6 10.1 18.4 340.0 48.5 43.4 43.4 42.9 41.9 41.2 47.8 43.1 42.7 41.3 40.5 39.7 103.8 139.6 94.1 85.0 75.8 55.6 61.9 49.9 45.8 56.1 54.1 52.4 -1,022.0 -842.6 -1,089.0 -241.8 0.0 -110.5 -393.5 0.0 0.0 -432.8 -453.5 -490.1 0.0 -215.7 -239.0 -279.8 -257.9 -301.0 -344.9 -272.1 -292.9 -334.6 -315.4 -352.5 -377.9 -0.5 20.2 -7.4 -31.1 -53.8 -136.7 -109.7 -180.0 -214.7 -144.9 -165.4 -186.2

MW 162.1 132.1 180.2 18.0 29.0 28.0 44.0 28.0 32.0 60.1 74.1 102.1 2.0 58.1 72.1 100.2 86.1 114.2 142.2 60.1 74.1 102.2 88.1 116.2 144.3 56.1 42.1 56.1 70.1 84.2 98.2 126.2 112.2 140.3 154.3 168.3 182.3

SG 1.1 1.3 1.2 1.0 0.9 0.3 0.3 0.3 0.3 1.1 1.0 0.9 0.3 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.6 0.5 0.6 0.7 0.7 0.8 0.7 0.8 0.8 0.8 0.8 0.8

ZC 0.28 0.22 0.32 0.23 0.31 0.30 0.27 0.29 0.29 0.21 0.22 0.24 0.31 0.23 0.25 0.25 0.27 0.25 0.24 0.25 0.25 0.26 0.26 0.27 0.26 0.28 0.28 0.27 0.27 0.26 0.27 0.25 0.27 0.28 0.25 0.25 0.25

156 TBP (C) -0.5 36.1 68.7 98.4 125.7 150.8 174.2 195.9 216.3 235.5 VLSTD (cm3/mol) 99.7 114.7 130.1 146.0 162.0 178.2 194.3 210.5 226.9 243.1

COMPONENT API DHFORM (kJ/mol) C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C11H24 C12H26 C13H28 CACO3 CA(CH-02 CA(CH-03 CA(OH)2 CAO CA(CH-01 XYLOS-01 SOLSL-01 SOLUN-01 LIGNI-01 BIOMA-01 110.6 92.8 81.6 74.1 68.7 64.6 61.2 58.6 56.5 54.6 -125.8 -146.8 -166.9 -187.6 -208.7 -228.7 -249.5 -270.4 -290.7 -311.8 0.0

MW 58.1 72.2 86.2 100.2 114.2 128.3 142.3 156.3 170.3 184.4 100.1 186.2 242.3 74.1 56.1 158.2 150.1 16.6 15.0 122.5 23.2

SG 0.6 0.6 0.7 0.7 0.7 0.7 0.7 0.7 0.8 0.8

ZC 0.27 0.27 0.27 0.26 0.26 0.26 0.25 0.25 0.25 0.25 0.20

-610.8 43.9 -1,040.0 -47.5 -119.0

0.20 3,396.9 0.20 441.9 552.3 552.3

The properties shown in Table C2 are: DHFORM: TBP: ZC: VLSTD: SG: MW: API: Formation Enthalpy True Normal Boiling Point Critical Compressibility Factor Standard Liquid Molar Volume at 60F Standard Specific Gravity at 60F Molecular Weight Standard API gravity

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APPENDIX C C.1 Mass Integration Literature review Several mass integration strategies can be used to develop cost-effective implementations. These strategies include stream segregation/mixing, recycle, interception using separation devices, changes in design and operating conditions of units, materials substitution, and technology changes including the use of alternate chemical pathways. These strategies can be classified into a hierarchy of three categories shown in Figure C-1: no-/low-cost changes, moderate cost modifications, and new technologies. (El-Halwagi, 2012)

Figure C-1. Hierarchy of mass-integration strategies. (El-Halwagi, 2012) C.1.1 Mass Integration Targeting Three sets of data for that species are first collected: fresh usage, terminal discharge, and generation/depletion. The fresh usage (F) refers to the amount of the targeted species in the streams entering the process (the waste stream may have entered the process as a fresh feedstock or a material utility). The terminal discharge (T) corresponds to the load of the targeted species in streams designated as waste streams or point sources for pollution.

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Generation (G) refers to the net amount of the targeted species, which is produced through chemical reaction. Depletion (D) may take place through chemical reactions but it may also be attributed to leaks, fugitive emissions, and other losses that are not explicitly accounted for. The net generation (Net_G) of a targeted species is defined as the difference between generation (G) and depletion (D). Superscripts indicate the stated of the stream, AMI means after mass integration, AFR after reduction that means the minimum load of the targeted species, AGMIN means after minimization of net generation. To minimize the terminal discharge of the targeted species, we should recycle the maximum amount from terminal streams (or paths leading to terminal streams) to replace fresh feed. When the target is minimize the fresh usage then the net generation must be maximize, like in Figure C-2, but when the target is minimize the waste discharge, the net generation must be minimum, and the Figure C-2 is different for minimize the net generation. The third case that can be present is when the net generation is no altered, then the target procedures for minimize waste discharge or fresh usage become identical. (ElHalwagi, 2012)

Figure C-2. Targeting for minimum usage of material utilities. (El-Halwagi, 2012)

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APPENDIX D D.1 Heat integration literature review The basic idea for heat integration is that there are process streams and units that need to be heated and other process streams and units that need to be cooled. Before using external Utilities to provide the necessary heating and cooling, heat integration seeks to transfer the heat from the process hot streams and units to the process cold streams and units. The remaining heating and cooling tasks are then fulfilled using the external heating and cooling Utilities. Figure D-1 is a schematic representation of a heat exchange network (HEN), where there are a given number NH of process hot streams (to be cooled) and a number NC of process cold streams (to be heated), also are the heat capacity (flow rate x specific heat) of each process hot stream, temperature and its supply (inlet) temperature, ; and its target (outlet)

. In addition, the heat capacity,

, and supply and target temperatures,

, are given for each process cold stream. (El-Halwagi, 2012)

Figure D-1. Synthesis of HEN. (El-Halwagi, 2012)

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D.1.1 Thermal Pinch Diagram One method to accomplish the minimum usage of heating and cooling Utilities, is the thermal pinch diagram, the first step is creating a global representation for all the hot streams by plotting the enthalpy exchanged by each process hot stream versus its temperature. Hence, a hot stream losing sensible heat is represented as an arrow whose tail to its supply temperature and its head corresponds to its target temperature. Assuming constant heat capacity over the operating range, the slope of each arrow is equal to .

The vertical distance between the tail and the head of each arrow represents the enthalpy lost by that hot stream according to (El-Halwagi , 2012):

(D-1)

(El-Halwagi , 2012)

Similar plot is doing for a cold stream, but a cold temperature scale, t, is created in one to one correspondence with the hot temperature scale, T using: (D-2) Where, (El-Halwagi , 2012)

is the minimum heat exchange driving force, for be feasible the heat

exchanger. And, instead a heat lost, in cold streams is a heat gained, by:

(D-3)

(El-Halwagi , 2012)

Next, both composite streams are plotted separate, and after, passed on the same diagram, the thermodynamic feasibility of heat exchange is guaranteed, when, the cold composite stream is located to the left of the hot composite stream; the point where the two composite streams touch is called the thermal pinch point, as Figure D-2.

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Figure D-2. Thermal pinch diagram. (El-Halwagi, 2012)

D.1.2 Cascade Diagram Another method to achieve the minimum usage of heating and cooling utilities is the cascade diagram, the first step is constructing a temperature-interval diagram (TID), and two corresponding temperature scales are generated: hot and cold, using Eq.D-2. Each stream is represented as a vertical arrow whose tail corresponds to its supply temperature, while its head represents its target temperature. Next, horizontal lines are drawn at the heads and tails of the arrows. These horizontal lines define a series of temperature intervals, z. Within any interval, it is thermodynamically feasible to transfer heat from the hot streams to the cold streams. Next, we construct a table of exchangeable heat loads (TEHL) to determine the heat-exchange loads of the process streams in each temperature interval. The exchangeable load of the uth hot stream (losing sensible heat) that passes through the zth interval is defined as: (D-4) (El-Halwagi , 2012)

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Where

and

are the hot-scale temperatures at the top and the bottom lines

defining the zth interval. On the other hand, the exchangeable capacity of the vth cold stream (gaining sensible heat) that passes through the zth interval is computed through,

(D-5)

(El-Halwagi, 2012)

The collective load of hot and cold process streams within the zth interval is calculated by summing up the individual loads of the hot or cold process streams that pass through that interval. Hence, for the zth temperature interval, one can write the following heat-balance equation: (D-6) (El-Halwagi ,2012)

Where

and

are the residual heats entering and leaving the zth interval. Figure

D-3 illustrates the heat balance around the zth temperature interval.

Figure D-3. Heat balance around a temperature interval. (El-Halwagi, 2012)

When,

is negative the residual heat is flowing upward, which is

thermodynamically infeasible. All negative residual heats can be made nonnegative if a hot

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load equal to the most negative

is added to the problem. This load is referred to as the . Once this hot load is added, the cascade

minimum heating utility requirement,

diagram is revised see Figure D-4. A zero residual heat designates the thermal pinch location. The load leaving the last temperature interval is the minimum cooling utility requirement, (El-Halwagi, 2012)

Figure D-4. Revised cascade diagram. (El-Halwagi, 2012)

D.1.3 Grand composite curve and Synthesis of HEN To minimize the cost of Utilities, it may be necessary to stage the use of Utilities such that at each level the use of the cheapest utility (USD/kJ) is maximized while ensuring its feasibility. A convenient way of screening multiple Utilities is the grand composite curve (GCC) as shown in Figure D-5.

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Figure D-5. Grand composite curve. (El-Halwagi, 2012)

The minimum operating cost (MOC) is a systematic method for the matching of hot and cold streams to synthesize a network of heat exchangers that satisfy the identified targets for minimum heating and cooling Utilities. The target for the minimum number of heat exchangers satisfying the MOC is given by,

(D-7) (El-Halwagi, 2012) Where, (D-8) (D-9)

is the number of MOC units above the pinch = is the number of hot streams (including heating Utilities) above the pinch, = is the number of cold streams (including cooling Utilities) above the pinch, = is the number of independent problems above the pinch,

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To determine the specific matches satisfying these targets, the design is started at the pinch and moved away according to the following rules.

, the number of hot streams or branches immediately above the pinch, must be less than the number of cold streams or branches immediately above the pinch.

, the number of cold streams or branches immediately below the pinch, must be less than the number of hot streams or branches immediately below the pinch

, Immediately above the pinch. , Immediately below the pinch

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APPENDIX E E.1 Economic literature review E.1.1 Types of cost As El-Halwagi (2012) explain in his book in chapter 2. For make a plant economic evaluation, two types of cost must be calculated: the capital cost and the operating cost. The first one, also called the total capital investment (TCI) is the money needed to purchase and install the plant; once the plant is in production mode, then the continuous expenses needed to run the plant are referred to as the operating costs. E.1.1.1 Capital cost Figure E-1 is a summary of the main components constituting the TCI, which is the sum of the fixed capital investment (FCI) and the working capital investment (WCI). The manufacturing FCI involves the fixed-cost items that are directly associated with production such as the processing equipment, installation, piping, pumping/compression, process instrumentation, process utility facilities and distribution, process waste treatment systems, and all the civil work associated with the production units. The nonmanufacturing FCI includes the fixed-cost items that are not directly tied to production such as land, analytical laboratories, storage areas, nonprocess utilities and waste treatment, engineering centers, research and development laboratories, administrative offices, cafeterias and restaurants, and recreational facilities. On the other hand, WCI is the money needed to pay for the operating expenditures up to the time when the product is sold as well as the expenses required to pay for stockpiling raw materials before production.

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WCI is recoverable at the end of the project. Typically, the WCI ranges between 10 percent and 25 percent of the TCI. (El-Halwagi 2012)

Figure E-1. Main components of TCI. (El-Halwagi, 2012) Some methods are used for TCI estimation: Manufactures quotation Computer-aided tools, for example Aspen Process Economic Analyzer (AEA) Capacity ratio with exponent, for example the six tenths factor rule shown in Equation F1, where m is the scaling factor, in Table E-1 are shown scaling factors for some equipment. (E-1) (Seider, Seader, & Lewin, 2004)

Updates using cost indices with Equation E-2, for example the Chemical Engineering Plant Cost Index (CE), the Nelson-Farrer Refinery Construction Index (NF) or the Marshall and Swift Cost Index (MS). Figure E-2 shown the cost index for different years. (E-2) (Towler & Sinnott, 2013)

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Ratio factors based on delivered equipment cost, for example Langs factor can be used for calculated de FCI based on Equation E-3. According to Seider, (2004) these factors depends on the extent to which the plant processes solids or fluids, Table E-2 shown this factors. (E-3) (El-Halwagi, 2012) Empirical correlations Turnover ratio Table E-1. Scaling factors to estimated equipment cost at various sizes. (Pham et al., 2012)

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Figure E-2. Variation of major cost indices. (Towler & Sinnott, 2013)

Table E-2. Lang factors for calculate capital cost. (Seider et al., 2004) Direct cost Purchased equipment Equipment installation Instrumentation and control Piping Electrical systems Buildings (including services) Yard improvements Services facilities Land Total direct plant cost Indirect cost Engineering and supervision Construction expenses Legal expenses Contractor's fees Contingency Total indirect plant cost Fixed capital investment (FCI) Working capital investment (WCI) Total capital investment (TCI) FCI Factor Fluid 100 47 36 68 11 18 10 70 360 33 41 4 22 44 144 504 89 593 5,04 Solid-fluid 100 39 26 31 10 29 12 55 302 32 34 4 19 37 126 428 75 503 4,28

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Equipment cost The equipment cost can divide in three types: Free on board (FOB): This is the cost of the equipment at the manufacturers loading docks, shipping trucks, rail cars, or barges at the vendors fabrication facility. Delivered equipment cost: This term corresponds to the equipment cost delivered to the buyer. It is the sum of the FOB and the delivery costs. Installed equipment cost: This is the sum of the delivered equipment cost plus the installation costs. (El-Halwagi, 2012)

E.1.1.2 Operating cost According to El-Halwagi, (2012) Items such as raw materials, material utilities, energy utilities, labor, and maintenance are among the key expenses for the operating cost. This cost can be divided in Fixed operating cost (FOC) and Variable operating cost (VOC), Table E-3 show the FOC and how to estimated, while the VOC are the feedstock, chemical and utilities cost.

Table E-3. Fixed Operating cost. (Seider et al., 2004) Labor Direct wage and benefits (DW&B) Direct salary and benefits Operating supplies and services Technical asistants to manufacturing control laboratory Maintenance Maintenance wages and benefits (MW&B) Salaries and benefits Materials and services Maintenance overhead

USD30,000 /operator -h 15% of DW&B 6% of DW&B USD 52,000 / operator/shift/year USD57,000 / operator/shift/year 3.5% of FCI 25% of MW&B 100% of MW&B 5% of MW&B

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Operating overhead General plant overhead 7.1% of M&O-SW&B* Mechanical department services 2.4% of M&O-SW&B Employee relations department 5.9% of M&O-SW&B Business services 7.4% of M&O-SW&B *M&O-SW&B: Maintenance and operations salary, wages and benefits

E.1.2 Depreciation and annualized fixed cost Depreciation is an annual income tax deduction that is intended to allow the company to recover the cost of property (for example, process equipment) over a certain recovery period. The following methods are for calculate depreciation. Linear (straight-line) method When depreciation is referred to the distribution of the depreciable FCI over the useful life period of the plant, is the annualized fixed cost (AFC), given by: (E-4) (El-Halwagi, 2012)

Where, FCI0 is the initial value of the depreciable FCI, FCIs is the salvage value of the FCI at the end of the service life, and N is the service life of the property in years. (El Halwagi, 2012) Declining-balance method According to El-Halwagi, (2012), the declining-balance method is an accelerated depreciation scheme in which the annual depreciation charge is taken as a fixed fraction of the book value at the end of the previous year. In Figure E-3 is shown the scheme for evaluated the depreciation charges and the book values over the recovery period of the project. Where,

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is the fixed depreciation fraction, two values of are commonly used: 1.5/n (for decliningbalance method or 150%) and 2/n (for double declining balance [DDB] or 200%) dn is a depreciation charge for the nth year n is a specific year in the life of the project N is the recovery period (or the last year in the recovery period) Vo is the initial value of the property Vn is the book value of the property at the end of year n Vs is the salvage value of the property at the end of the recovery period (N years) Book Value at Beginning of the Year Vo (1-) Vo Book Value at End of the Year (1-) Vo (1-)2 Vo

Year 1 2 . n

Depreciation Charge Vo (1-) Vo

(1-)n-1 Vo

(1-)n-1 Vo

(1-)n Vo

Figure E-3. Depreciation charges and the book values. (El-Halwagi, 2012)

Modified accelerated cost recovery system (MACRS). E.1.3 Profitability analysis E.1.3.1 Profitability analysis without the time of value of money As El-Halwagi, (2012) said, two criteria are commonly used for assessing the profitability of a project without including interest or the time value of money, the return on investment (ROI) and payback period.

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Return on investment (ROI): ROI has the units of percentage per year. It is analogous (and should be compared) to interest rates from banks and return on investment from investments in the financial markets. Clearly, the higher the ROI, the more desirable the project. In many cases, a hurdle rate of 10 to 15 percent for the ROI is required.

(E-5) (El-Halwagi, 2012) Where,

The annual income tax for Seider, (2004) is 37%, and for Pham, (2012) is 39%. Payback period (PBP): The PBP is the time required for the annual earnings to equal the original investment.

(E-6) (Seider et al., 2004)

Venture Profit (VP): Seider, (2004) include other criteria for calculated an approximate profitability, the VP is annual net earnings in excess of a minimum acceptable return of investment imin. (E-7) (Seider et al., 2004)

E.1.3.2 Profitability analysis with the time of value of money When the time-value of money is considered, the following profitability criteria may be used: Net Present Value (NPV): NPV is the cumulative value (revenues expenses) adjusted to the reference time. The present time may be taken as the beginning of expenditures

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or the start of operation. Figure F5 show the cash flow with NPV at the beginning of expenditures. (E-8) (El-Halwagi, 2012) Where, AFCN is the annual cash flow for year N, (which may be negative in the case of outflows or positive in the case of inflows). AFCN is defined as:

(E-9) The term

(El-Halwagi, 2012)

is referred to as the discount factor, and i is called the discount rate.

Figure E-4. Cash flow diagram with NPV. (El-Halwagi, 2012)

An annuity (A) is a series of constant payments or withdrawals made at equal time intervals. It is commonly used in the payment of FCI over a period of time, home mortgages, savings as part of a retirement plan, life insurance. Shown below is the future sum of the annuity after N period as a function of the uniform annuity payments, the interest rate, and the N time periods.

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(E-10) (El-Halwagi, 2012) We get the present sum of the annuity, P, as: (E-11) (El-Halwagi, 2012) Where, AFC/FCI is called the capital recovery factor or the annual capital charge ratio

Discounted cash flow return on investment: The discounted cash flow return on investment is also known as the internal rate of return (IRR), and is the value of i that renders the NPV to be zero. As such, the IRR provides the ROI for the project when the time-value of money is considered and when all expenses and revenues are accounted for over the life period of the project. The higher the value of the IRR, the more attractive the project is. (El-Halwagi, 2012)

E.1.4 Prices of Products and Feedstock

Figure E-5. Crude Oil price. (EIA, 2013)

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Figure E-6. Diesel price. (EIA, 2013)

Figure E-7. Jet price. (EIA, 2013)

Figure E-8. Gasoline price. (EIA, 2013)

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VITA

Laura Prada was born in Bucaramanga (Colombia). She grew up in the city called the parks city, located at 5 hours of Venezuela. She attended at Universidad Industrial de Santander (Bucaramanga, Colombia) where she received a Bachelor of Science in chemical engineering in 2003. Once she finished her undergraduate studies, she work for almost three years in biofuels and hydrotreating at Colombian Petroleum Institute (ICP), the research and development of Ecopetrol in Bucaramanga. After that, she moved to Bogot and work for almost four years like process engineer at the company HMV ingenieros. She entered the graduate program at Universidad de los Andes (Bogot) in August 2011, and graduated with a Master of Science in Chemical Engineering in 2013. Her thesis was study the retrofitting analysis of biofuels in fossil fuels process, with the simulation of some Aspen suites.

Laura Patricia Prada Villamizar C/O Dr. Rocio Sierra Ramrez Department of Chemical Engineering Universidad de los Andes Cra 1 Este No 19A 40 (Bogot, Colombia)