Table Of ContentGREEN CHEMISTRY AND CHEMICAL ENGINEERING
CCHHEEMMIICCAALLSS FFRROOMM BBIIOOMMAASSSS
IInntteeggrraattiinngg BBiioopprroocceesssseess iinnttoo
CChheemmiiccaall PPrroodduuccttiioonn CCoommpplleexxeess
ffoorr SSuussttaaiinnaabbllee DDeevveellooppmmeenntt
DDEEBBAALLIINNAA SSEENNGGUUPPTTAA
RRAALLPPHH WW.. PPIIKKEE
CHEMICALS FROM BIOMASS
Integrating Bioprocesses into
Chemical Production Complexes
for Sustainable Development
GREEN CHEMISTRY AND CHEMICAL ENGINEERING
Series Editor: Sunggyu Lee
Ohio University, Athens, Ohio, USA
Proton Exchange Membrane Fuel Cells: Contamination and Mitigation Strategies
Hui Li, Shanna Knights, Zheng Shi, John W. Van Zee, and Jiujun Zhang
Proton Exchange Membrane Fuel Cells: Materials Properties and Performance
David P. Wilkinson, Jiujun Zhang, Rob Hui, Jeffrey Fergus, and Xianguo Li
Solid Oxide Fuel Cells: Materials Properties and Performance
Jeffrey Fergus, Rob Hui, Xianguo Li, David P. Wilkinson, and Jiujun Zhang
Efficiency and Sustainability in the Energy and Chemical Industries:
Scientific Principles and Case Studies, Second Edition
Krishnan Sankaranarayanan, Jakob de Swaan Arons, and Hedzer van der Kooi
Nuclear Hydrogen Production Handbook
Xing L. Yan and Ryutaro Hino
Magneto Luminous Chemical Vapor Deposition
Hirotsugu Yasuda
Carbon-Neutral Fuels and Energy Carriers
Nazim Z. Muradov and T. Nejat Vezirogˇlu
Oxide Semiconductors for Solar Energy Conversion: Titanium Dioxide
Janusz Nowotny
Lithium-Ion Batteries: Advanced Materials and Technologies
Xianxia Yuan, Hansan Liu, and Jiujun Zhang
Process Integration for Resource Conservation
Dominic C. Y. Foo
Chemicals from Biomass: Integrating Bioprocesses into Chemical Production Complexes
for Sustainable Development
Debalina Sengupta and Ralph W. Pike
GREEN CHEMISTRY AND CHEMICAL ENGINEERING
CHEMICALS FROM BIOMASS
Integrating Bioprocesses into
Chemical Production Complexes
for Sustainable Development
DEBALINA SENGUPTA
RALPH W. PIKE
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2013 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20120530
InternationalStandardBookNumber-13:978-1-4398-7815-6(eBook-PDF)
This book contains information obtained from authentic and highly regarded sources. Reasonable
efforts have been made to publish reliable data and information, but the author and publisher cannot
assume responsibility for the validity of all materials or the consequences of their use. The authors and
publishers have attempted to trace the copyright holders of all material reproduced in this publication
and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any
future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced,
transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or
hereafter invented, including photocopying, microfilming, and recording, or in any information stor-
age or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copy-
right.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222
Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that pro-
vides licenses and registration for a variety of users. For organizations that have been granted a pho-
tocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice:Product or corporate names may be trademarks or registered trademarks, and are
used only for identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Contents
Series Preface..........................................................................................................xi
Preface...................................................................................................................xiii
Authors................................................................................................................xvii
1. Introduction.....................................................................................................1
1.1 Introduction...........................................................................................1
1.2 Research Vision.....................................................................................3
1.3 New Frontiers........................................................................................4
1.4 Chemical Industry in the Lower Mississippi River Corridor.........5
1.5 Criteria for the Optimal Configuration of Plants.............................9
1.6 Optimization of Chemical Complex................................................10
1.7 Contributions of This Methodology.................................................13
1.8 Organization of Chapters..................................................................14
1.9 Summary..............................................................................................18
2. BiomassasFeedstock...................................................................................21
2.1 Introduction.........................................................................................21
2.2 Biomass Formation.............................................................................25
2.2.1 Calvin–Benson Cycle.............................................................26
2.2.2 C4 Cycle...................................................................................26
2.2.3 CAM Cycle..............................................................................26
2.3 Biomass Classification and Composition........................................27
2.3.1 Saccharides and Polysaccharides........................................27
2.3.2 Starch.......................................................................................28
2.3.3 Lignocellulosic Biomass........................................................29
2.3.4 Lipids, Fats, and Oils.............................................................31
2.3.5 Proteins....................................................................................31
2.4 Biomass Conversion Technologies....................................................32
2.4.1 Biomass Pretreatment...........................................................33
2.4.2 Fermentation...........................................................................35
2.4.3 Anaerobic Digestion..............................................................36
2.4.4 Transesterification..................................................................39
2.4.5 Gasification/Pyrolysis...........................................................44
2.5 Biomass Feedstock Availability........................................................46
2.5.1 Forest Resources.....................................................................48
2.5.1.1 Forestland Base.......................................................48
2.5.1.2 Types of Forest Resource.......................................48
2.5.1.3 Limiting Factors for Forest Resource
Utilization................................................................51
2.5.1.4 Summary for Forest Resources............................51
v
vi Contents
2.5.2 Agricultural Resources.........................................................52
2.5.2.1 Agricultural Land Base.........................................52
2.5.2.2 Types of Agricultural Resource...........................53
2.5.2.3 Limiting Factors for Agricultural Resource
Utilization................................................................56
2.5.2.4 Summary for Agricultural Resources.................58
2.5.3 Aquatic Resources..................................................................58
2.5.3.1 Recent Trends in Algae Research.........................60
2.5.3.2 Algae Species..........................................................63
2.6 Summary..............................................................................................65
3. ChemicalsfromBiomass.............................................................................67
3.1 Introduction.........................................................................................67
3.2 Chemicals from Nonrenewable Resources.....................................68
3.3 Chemicals from Biomass as Feedstock............................................70
3.4 Biomass Conversion Products (Chemicals).....................................73
3.4.1 Single-Carbon Compounds..................................................73
3.4.1.1 Methane...................................................................73
3.4.1.2 Methanol..................................................................74
3.4.2 Two-Carbon Compounds.....................................................76
3.4.2.1 Ethanol.....................................................................76
3.4.2.2 Acetic Acid..............................................................87
3.4.2.3 Ethylene...................................................................88
3.4.3 Three-Carbon Compounds..................................................91
3.4.3.1 Glycerol....................................................................91
3.4.3.2 Lactic Acid...............................................................93
3.4.3.3 Propylene Glycol.....................................................93
3.4.3.4 1,3-Propanediol.......................................................94
3.4.3.5 Acetone....................................................................95
3.4.4 Four-Carbon Compounds....................................................95
3.4.4.1 Butanol.....................................................................95
3.4.4.2 Succinic Acid...........................................................96
3.4.4.3 Aspartic Acid..........................................................98
3.4.5 Five-Carbon Compounds.....................................................98
3.4.5.1 Levulinic Acid........................................................98
3.4.5.2 Xylitol/Arabinitol..................................................100
3.4.5.3 Itaconic Acid..........................................................100
3.4.6 Six-Carbon Compounds......................................................102
3.4.6.1 Sorbitol...................................................................102
3.4.6.2 2,5-Furandicarboxylic Acid.................................102
3.5 Biopolymers and Biomaterials........................................................103
3.6 Natural-Oil-Based Polymers and Chemicals................................105
3.7 Summary............................................................................................108
Contents vii
4. SimulationforBioprocesses.....................................................................111
4.1 Introduction.......................................................................................111
4.2 Ethanol Production from Corn Stover Fermentation...................115
4.2.1 Process Description for Ethanol Production
from Corn Stover Fermentation.........................................116
4.2.1.1 Pretreatment Section............................................119
4.2.1.2 Fermentation Section...........................................121
4.2.1.3 Purification Section..............................................122
4.2.2 Process Cost Estimation for Ethanol Production
from Corn Stover Fermentation.........................................125
4.2.3 Summary of Ethanol Production from Corn Stover
Fermentation.........................................................................128
4.3 Ethylene Production from Dehydration of Ethanol.....................128
4.3.1 Process Description for Ethylene Production
from Dehydration of Ethanol.............................................129
4.3.2 Process Cost Estimation for Ethylene Production
from Dehydration of Ethanol.............................................131
4.3.3 Summary of Ethylene Production from Dehydration
of Ethanol..............................................................................133
4.4 Fatty Acid Methyl Ester and Glycerol
from Transesterification of Soybean Oil........................................134
4.4.1 Process Description for Fatty Acid Methyl Ester
andGlycerolfromTransesterificationofSoybeanOil....137
4.4.1.1 Transesterification Section..................................140
4.4.1.2 Methyl Ester Purification Section......................141
4.4.1.3 Glycerol Recovery and Purification...................141
4.4.2 ProcessCostEstimationforFattyAcidMethylEster
andGlycerolfromTransesterificationofSoybeanOil.....144
4.4.3 Summary of Fatty Acid Methyl Ester and Glycerol
from Transesterification of Soybean Oil...........................146
4.5 PropyleneGlycolProductionfromHydrogenolysisofGlycerol....147
4.5.1 Process Description for Propylene Glycol Production
from Hydrogenolysis of Glycerol......................................147
4.5.2 Process Cost Estimation for Propylene
Glycol Production from Hydrogenolysis of Glycerol.....150
4.5.3 Summary of Propylene Glycol Production from
Hydrogenolysis of Glycerol................................................152
4.6 AceticAcidProductionfromCornStoverAnaerobicDigestion....152
4.6.1 Process Description for Acetic Acid Production
from Corn Stover Anaerobic Digestion............................154
4.6.1.1 Pretreatment Section............................................154
4.6.1.2 Anaerobic Digestion Section..............................158
4.6.1.3 Purification and Recovery Section.....................160
viii Contents
4.6.2 Process Cost Estimation for Acetic Acid Production
from Corn Stover Anaerobic Digestion............................163
4.6.3 Summary of Acetic Acid Production from Corn
Stover Anaerobic Digestion................................................165
4.7 Ethanol Production from Corn Dry-Grind Fermentation...........165
4.8 Summary............................................................................................170
5. BioprocessesPlantModelFormulation.................................................171
5.1 Introduction.......................................................................................171
5.2 Ethanol Production from Corn Stover Fermentation...................174
5.2.1 Pretreatment (Corn Stover).................................................175
5.2.2 Fermentation (Corn Stover)................................................180
5.2.3 Purification Section (Corn Stover EtOH)..........................181
5.3 Ethanol Production from Corn Dry-Grind Fermentation...........196
5.3.1 Pretreatment (Corn).............................................................197
5.3.2 Fermentation (Corn)............................................................201
5.3.3 Purification (Corn EtOH)....................................................201
5.4 Ethylene Production from Dehydration of Ethanol.....................209
5.5 AceticAcidProductionfromCornStover
AnaerobicDigestion.........................................................................212
5.5.1 Pretreatment (Corn Stover) Anaerobic Digestion............216
5.5.2 Anaerobic Digestion............................................................217
5.5.3 Purification (Acetic Acid)....................................................219
5.6 Fatty Acid Methyl Ester and Glycerol
from Transesterification of Natural Oil.........................................225
5.7 PropyleneGlycolProductionfromHydrogenolysis
ofGlycerol.........................................................................................232
5.8 Algae Oil Production........................................................................235
5.9 Gasification of Corn Stover..............................................................239
5.10 Summary of Bioprocess Model Formulation................................242
5.11 Interconnections for Bioprocesses..................................................244
5.12 Summary............................................................................................246
6. FormulationandOptimizationoftheSuperstructure.......................247
6.1 Introduction.......................................................................................247
6.2 Integrated Biochemical and Chemical Production
Complex Optimization.....................................................................247
6.3 Binary Variables and Logical Constraints for MINLP................255
6.4 Constraints for Capacity and Demand..........................................257
6.5 Optimization Economic Model—Triple Bottom Line..................259
6.6 Optimal Structure.............................................................................265
6.7 Multiobjective Optimization of the Integrated
Biochemical Production Complex..................................................274
