Jhuma Sadhukhan, Kok Siew Ng, Elias Martinez Hernandez
Biorefineries and Chemical Processes
Design, Integration and Sustainability Analysis
Jhuma Sadhukhan, Kok Siew Ng, Elias Martinez Hernandez
Biorefineries and Chemical Processes
Design, Integration and Sustainability Analysis
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As the range of feedstocks, process technologies and products expand, biorefineries will become increasingly complex manufacturing systems. B iorefineries and Chemical Processes: Design, Integration and Sustainability Analysis presents process modelling and integration, and whole system life cycle analysis tools for the synthesis, design, operation and sustainable development of biorefinery and chemical processes.
Topics covered include:
Introduction: An introduction to the concept and development of biorefineries.
Tools: Included here are the methods for detailed economic and…mehr
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As the range of feedstocks, process technologies and products expand, biorefineries will become increasingly complex manufacturing systems. B iorefineries and Chemical Processes: Design, Integration and Sustainability Analysis presents process modelling and integration, and whole system life cycle analysis tools for the synthesis, design, operation and sustainable development of biorefinery and chemical processes.
Topics covered include:
Introduction: An introduction to the concept and development of biorefineries.
Tools: Included here are the methods for detailed economic and environmental impact analyses; combined economic value and environmental impact analysis; life cycle assessment (LCA); multi-criteria analysis; heat integration and utility system design; mathematical programming based optimization and genetic algorithms.
Process synthesis and design: Focuses on modern unit operations and innovative process flowsheets. Discusses thermochemical and biochemical processing of biomass, production of chemicals and polymers from biomass, and processes for carbon dioxide capture.
Biorefinery systems: Presents biorefinery process synthesis using whole system analysis. Discusses bio-oil and algae biorefineries, integrated fuel cells and renewables, and heterogeneous catalytic reactors.
Companion website: Four case studies, additional exercises and examples are available online, together with three supplementary chapters which address waste and emission minimization, energy storage and control systems, and the optimization and reuse of water.
This textbook is designed to bridge a gap between engineering design and sustainability assessment, for advanced students and practicing process designers and engineers.
Hinweis: Dieser Artikel kann nur an eine deutsche Lieferadresse ausgeliefert werden.
Topics covered include:
Introduction: An introduction to the concept and development of biorefineries.
Tools: Included here are the methods for detailed economic and environmental impact analyses; combined economic value and environmental impact analysis; life cycle assessment (LCA); multi-criteria analysis; heat integration and utility system design; mathematical programming based optimization and genetic algorithms.
Process synthesis and design: Focuses on modern unit operations and innovative process flowsheets. Discusses thermochemical and biochemical processing of biomass, production of chemicals and polymers from biomass, and processes for carbon dioxide capture.
Biorefinery systems: Presents biorefinery process synthesis using whole system analysis. Discusses bio-oil and algae biorefineries, integrated fuel cells and renewables, and heterogeneous catalytic reactors.
Companion website: Four case studies, additional exercises and examples are available online, together with three supplementary chapters which address waste and emission minimization, energy storage and control systems, and the optimization and reuse of water.
This textbook is designed to bridge a gap between engineering design and sustainability assessment, for advanced students and practicing process designers and engineers.
Hinweis: Dieser Artikel kann nur an eine deutsche Lieferadresse ausgeliefert werden.
Produktdetails
- Produktdetails
- Verlag: Wiley & Sons
- 1. Auflage
- Seitenzahl: 688
- Erscheinungstermin: 27. Oktober 2014
- Englisch
- Abmessung: 246mm x 189mm x 36mm
- Gewicht: 1118g
- ISBN-13: 9781119990864
- ISBN-10: 1119990866
- Artikelnr.: 40077933
- Herstellerkennzeichnung
- Libri GmbH
- Europaallee 1
- 36244 Bad Hersfeld
- 06621 890
- Verlag: Wiley & Sons
- 1. Auflage
- Seitenzahl: 688
- Erscheinungstermin: 27. Oktober 2014
- Englisch
- Abmessung: 246mm x 189mm x 36mm
- Gewicht: 1118g
- ISBN-13: 9781119990864
- ISBN-10: 1119990866
- Artikelnr.: 40077933
- Herstellerkennzeichnung
- Libri GmbH
- Europaallee 1
- 36244 Bad Hersfeld
- 06621 890
Jhuma Sadhukhan Centre for Environmental Strategy, University of Surrey, UK Kok Siew Ng Centre for Process Integration, The University of Manchester, UK Elias Martinez H. Centre for Environmental Strategy, University of Surrey, UK
Preface xiii
Acknowledgments xvii
About the Authors xxi
CompanionWebsite xxiii
Nomenclature xxv
I INTRODUCTION 1
1 Introduction 3
1.1 Fundamentals of the Biorefinery Concept 3
1.1.1 Biorefinery Principles 3
1.1.2 Biorefinery Types and Development 4
1.2 Biorefinery Features and Nomenclature 5
1.3 Biorefinery Feedstock: Biomass 7
1.3.1 Chemical Nature of Biorefinery Feedstocks 8
1.3.2 Feedstock Characterization 10
1.4 Processes and Platforms 12
1.5 Biorefinery Products 15
1.6 Optimization of Preprocessing and Fractionation for Bio Based
Manufacturing 18
1.6.1 Background of Lignin 26
1.7 Electrochemistry Application in Biorefineries 31
1.8 Introduction to Energy and Water Systems 34
1.9 Evaluating Biorefinery Performances 36
1.9.1 Performance Indicators 36
1.9.2 Life Cycle Analysis 38
1.10 Chapters 38
1.11 Summary 38
References 39
II TOOLS 43
2 Economic Analysis 45
2.1 Introduction 45
2.2 General Economic Concepts and Terminology 46
2.2.1 Capital Cost and Battery Limits 46
2.2.2 Cost Index 46
2.2.3 Economies of Scale 47
2.2.4 Operating Cost 48
2.2.5 Cash Flows 49
2.2.6 Time Value of Money 49
2.2.7 Discounted Cash Flow Analysis and Net Present Value 50
2.2.8 Profitability Analysis 52
2.2.9 Learning Effect 53
2.3 Methodology 54
2.3.1 Capital Cost Estimation 54
2.3.2 Profitability Analysis 55
2.4 Cost Estimation and Correlation 55
2.4.1 Capital Cost 55
2.4.2 Operating Cost 58
2.5 Summary 59
2.6 Exercises 60
References 61
3 Heat Integration and Utility System Design 63
3.1 Introduction 63
3.2 Process Integration 64
3.3 Analysis of Heat Exchanger Network Using Pinch Technology 65
3.3.1 Data Extraction 66
3.3.2 Construction of Temperature-Enthalpy Profiles 69
3.3.3 Application of the Graphical Approach for Energy Recovery 76
3.4 Utility System 83
3.4.1 Components in Utility System 83
3.5 Conceptual Design of Heat Recovery System for Cogeneration 88
3.5.1 Conventional Approach 88
3.5.2 Heuristic Based Approach 88
3.6 Summary 91
References 91
4 Life Cycle Assessment 93
4.1 Life Cycle Thinking 93
4.2 Policy Context 96
4.3 Life Cycle Assessment (LCA) 96
4.4 LCA: Goal and Scope Definition 100
4.5 LCA: Inventory Analysis 104
4.6 LCA: Impact Assessment 111
4.6.1 Global Warming Potential 114
4.6.2 Land Use 115
4.6.3 Resource Use 119
4.6.4 Ozone Layer Depletion 121
4.6.5 Acidification Potential 123
4.6.6 Photochemical Oxidant Creation Potential 126
4.6.7 Aquatic Ecotoxicity 127
4.6.8 Eutrophication Potential 127
4.6.9 Biodiversity 128
4.7 LCA: Interpretation 128
4.7.1 Stand-Alone LCA 128
4.7.2 Accounting LCA 129
4.7.3 Change Oriented LCA 129
4.7.4 Allocation Method 129
4.8 LCIA Methods 130
4.9 Future R&D Needs 145
References 145
5 Data Uncertainty and Multicriteria Analyses 147
5.1 Data Uncertainty Analysis 147
5.1.1 Dominance Analysis 148
5.1.2 Contribution Analysis 149
5.1.3 Scenario Analysis 151
5.1.4 Sensitivity Analysis 153
5.1.5 Monte Carlo Simulation 154
5.2 Multicriteria Analysis 159
5.2.1 Economic Value and Environmental Impact Analysis of Biorefinery
Systems 160
5.2.2 Socioeconomic Analysis 163
5.3 Summary 165
References 165
6 Value Analysis 167
6.1 Value on Processing (VOP) and Cost of Production (COP) of Process
Network Streams 168
6.2 Value Analysis Heuristics 172
6.2.1 Discounted Cash Flow Analysis 173
6.3 Stream Economic Profile 175
6.4 Concept of Boundary and Evaluation of Economic Margin of a Process
Network 175
6.5 Stream Profitability Analysis 176
6.5.1 Value Analysis to Determine Necessary and Sufficient Condition for
Streams to be Profitable or Nonprofitable 181
6.6 Summary 187
References 187
7 Combined Economic Value and Environmental Impact (EVEI) Analysis 189
7.1 Introduction 189
7.2 Equivalency Between Economic and Environmental Impact Concepts 190
7.3 Evaluation of Streams 196
7.4 Environmental Impact Profile 200
7.5 Product Economic Value and Environmental Impact (EVEI) Profile 201
7.6 Summary 204
References 205
8 Optimization 207
8.1 Introduction 207
8.2 Linear Optimization 208
8.2.1 Step 1: Rewriting in Standard LP Format 210
8.2.2 Step 2: Initializing the Simplex Method 211
8.2.3 Step 3: Obtaining an Initial Basic Solution 212
8.2.4 Step 4: Determining Simplex Directions 212
8.2.5 Step 5: Determining the Maximum Step Size by the Minimum Ratio Rule
213
8.2.6 Step 6: Updating the Basic Variables 214
8.3 Nonlinear Optimization 218
8.3.1 Gradient Based Methods 219
8.3.2 Generalized Reduced Gradient (GRG) Algorithm 226
8.4 Mixed Integer Linear or Nonlinear Optimization 239
8.4.1 Branch and Bound Method 240
8.5 Stochastic Method 243
8.5.1 Genetic Algorithm (GA) 244
8.5.2 Non-dominated Sorting Genetic Algorithm (NSGA) Optimization 246
8.5.3 GA in MATLAB 248
8.6 Summary 248
References 248
III PROCESS SYNTHESIS AND DESIGN 251
9 Generic Reactors: Thermochemical Processing of Biomass 253
9.1 Introduction 253
9.2 General Features of Thermochemical Conversion Processes 254
9.3 Combustion 257
9.4 Gasification 258
9.4.1 The Process 258
9.4.2 Types of Gasifier 260
9.4.3 Design Considerations 260
9.5 Pyrolysis 262
9.5.1 What is Bio-Oil? 262
9.5.2 How Is Bio-Oil Obtained from Biomass? 264
9.5.3 How Fast Pyrolysis Works 265
9.6 Summary 270
Exercises 270
References 270
10 Reaction Thermodynamics 271
10.1 Introduction 271
10.2 Fundamentals of Design Calculation 272
10.2.1 Heat of Combustion 272
10.2.2 Higher and Lower Heating Values 276
10.2.3 Adiabatic Flame Temperature 278
10.2.4 Theoretical Air-to-Fuel Ratio 279
10.2.5 Cold Gas Efficiency 280
10.2.6 Hot Gas Efficiency 281
10.2.7 Equivalence Ratio 281
10.2.8 Carbon Conversion 282
10.2.9 Heat of Reaction 282
10.3 Process Design: Synthesis and Modeling 282
10.3.1 Combustion Model 282
10.3.2 Gasification Model 283
10.3.3 Pyrolysis Model 289
10.4 Summary 291
Exercises 291
References 292
11 Reaction and Separation Process Synthesis: Chemical Production from
Biomass 295
11.1 Chemicals from Biomass: An Overview 296
11.2 Bioreactor and Kinetics 297
11.2.1 An Example of Lactic Acid Production 299
11.2.2 An Example of Succinic Acid Production 304
11.2.3 Heat Transfer Strategies for Reactors 308
11.2.4 An Example of Ethylene Production 309
11.2.5 An Example of Catalytic Fast Pyrolysis 311
11.3 Controlled Acid Hydrolysis Reactions 318
11.4 Advanced Separation and Reactive Separation 327
11.4.1 Membrane Based Separations 327
11.4.2 Membrane Filtration 330
11.4.3 Electrodialysis 333
11.4.4 Ion Exchange 334
11.4.5 Integrated Processes 338
11.4.6 Reactive Extraction 341
11.4.7 Reactive Distillation 352
11.4.8 Crystallization 354
11.4.9 Precipitation 360
11.5 Guidelines for Integrated Biorefinery Design 360
11.5.1 An Example of Levulinic Acid Production: The Biofine Process 365
11.6 Summary 368
References 370
12 Polymer Processes 373
12.1 Polymer Concepts 374
12.1.1 Polymer Classification 375
12.1.2 Polymer Properties 376
12.1.3 From Petrochemical Based Polymers to Biopolymers 379
12.2 Modified Natural Biopolymers 385
12.2.1 Starch Polymers 385
12.2.2 Cellulose Polymers 389
12.2.3 Natural Fiber and Lignin Composites 389
12.3 Modeling of Polymerization Reaction Kinetics 391
12.3.1 Chain-Growth or Addition Polymerization 392
12.3.2 Step-Growth Polymerization 396
12.3.3 Copolymerization 398
12.4 Reactor Design for Biomass Based Monomers and Biopolymers 400
12.4.1 Plug Flow Reactor (PFR) Design for Reaction in Gaseous Phase 400
12.4.2 Bioreactor Design for Biopolymer Production - An Example of
Polyhydroxyalkanoates 402
12.4.3 Catalytic Reactor Design 403
12.4.4 Energy Transfer Models of Reactors 412
12.5 Synthesis of Unit Operations Combining Reaction and Separation
Functionalities 416
12.5.1 Reactive Distillation Column 416
12.5.2 An Example of a Novel Reactor Arrangement 418
12.6 Integrated Biopolymer Production in Biorefineries 421
12.6.1 Polyesters 421
12.6.2 Polyurethanes 422
12.6.3 Polyamides 422
12.6.4 Polycarbonates 424
12.7 Summary 424
References 424
13 Separation Processes: Carbon Capture 425
13.1 Absorption 426
13.2 Absorption Process Flowsheet Synthesis 429
13.3 The RectisolTM Technology 431
13.3.1 Design and Operating Regions of RectisolTM Process 433
13.3.2 Energy Consumption of a RectisolTM Process 435
13.4 The SelexolTM Technology 446
13.4.1 SelexolTM Process Parametric Analysis 448
13.5 Adsorption Process 457
13.5.1 Kinetic Modeling of SMR Reactions 458
13.5.2 Adsorption Modeling of Carbon Dioxide 460
13.5.3 Sorption Enhanced Reaction (SER) Process Dynamic Modeling Framework
460
13.6 Chemical Looping Combustion 463
13.7 Low Temperature Separation 471
13.8 Summary 472
References 473
IV BIOREFINERY SYSTEMS 475
14 Bio-Oil Refining I: Fischer-Tropsch Liquid and Methanol Synthesis 477
14.1 Introduction 477
14.2 Bio-Oil Upgrading 478
14.2.1 Physical Upgrading 478
14.2.2 Chemical Upgrading 478
14.2.3 Biological Upgrading 480
14.3 Distributed and Centralized Bio-Oil Processing Concept 481
14.3.1 The Concept 481
14.3.2 The Economics of Local Distribution of Bio-Oil 482
14.3.3 The Economics of Importing Bio-Oil from Other Countries 483
14.4 Integrated Thermochemical Processing of Bio-Oil into Fuels 483
14.4.1 Synthetic Fuel Production 484
14.4.2 Methanol Production 485
14.5 Modeling, Integration and Analysis of Thermochemical Processes of
Bio-Oil 486
14.5.1 Flowsheet Synthesis and Modeling 486
14.5.2 Sensitivity Analysis 488
14.6 Summary 494
References 494
15 Bio-Oil Refining II: Novel Membrane Reactors 497
15.1 Bio-Oil Co-Processing in Crude Oil Refinery 497
15.2 Mixed Ionic Electronic Conducting (MIEC) Membrane for Hydrogen
Production and Bio-Oil Hydrotreating and Hydrocracking 499
15.3 Bio-Oil Hydrotreating and Hydrocracking Reaction Mechanisms and a MIEC
Membrane Reactor Based Bio-Oil Upgrader Process Flowsheet 502
15.4 A Coursework Problem 510
15.5 Summary 513
References 514
16 Fuel Cells and Other Renewables 515
16.1 Biomass Integrated Gasification Fuel Cell (BGFC) System Modeling for
Design, Integration and Analysis 517
16.2 Simulation of Integrated BGFC Flowsheets 520
16.3 Heat Integration of BGFC Flowsheets 528
16.4 Analysis of Processing Chains in BGFC Flowsheets 529
16.5 SOFC Gibbs Free Energy Minimization Modeling 532
16.6 Design of SOFC Based Micro-CHP Systems 536
16.7 Fuel Cell and SOFC Design Parameterization Suitable for Spreadsheet
Implementation 537
16.7.1 Mass Balance 539
16.7.2 Electrochemical Descriptions 540
16.7.3 An air Blower Power Consumption 542
16.7.4 Combustor Modeling 543
16.7.5 Energy Balance 543
16.8 Summary 546
References 546
17 Algae Biorefineries 547
17.1 Algae Cultivation 548
17.1.1 Open Pond Cultivation 548
17.1.2 Photobioreactors (PBRs) 556
17.2 Algae Harvesting and Oil Extraction 562
17.2.1 Harvesting 562
17.2.2 Extraction 570
17.3 Algae Biodiesel Production 570
17.3.1 Biodiesel Process 570
17.3.2 Heterogeneous Catalysts for Transesterification 572
17.4 Algae Biorefinery Integration 572
17.5 Life Cycle Assessment of Algae Biorefineries 575
17.6 Summary 579
References 579
18 Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling:
Example of Biodiesel 581
18.1 Intrinsic Kinetic Modeling 582
18.1.1 Elementary Reaction Mechanism and Intrinsic Kinetic Modeling of the
Biodiesel Production System 582
18.1.2 Solution Strategy for the Rate Equations Resulting from the
Elementary Reaction Mechanism 590
18.1.3 Correlation between Concentration and Activity of Species Using the
UNIQUAC Contribution Method 591
18.1.4 An Example of EXCEL Spreadsheet Based UNIQUAC Calculation for a
Biodiesel Production System is Shown in Detail for Implementation in Online
Resource Material, Chapter 18 - Additional Exercises and Examples 592
18.1.5 Intrinsic Kinetic Modeling Framework 592
18.2 Diffusion Modeling 595
18.3 Multi-scale Mass Transfer Modeling 598
18.3.1 Dimensionless Physical Parameter Groups 606
18.4 Summary 612
References 612
V ONLINE RESOURCES
Web Chapter 1: Waste and Emission Minimization
Web Chapter 2: Energy Storage and Control Systems
Web Chapter 3: Water Reuse, Footprint and Optimization Analysis
Case Study 1: Biomass CHP Plant Design Problem - LCA and Cost Analysis
Case Study 2: Comparison between Epoxy Resin Productions from Algal or Soya
Oil - An LCA Based Problem Solving Approach
Case Study 3: Waste Water Sludge Based CHP and Agricultural Application
System - An LCA Based Problem Solving Approach
Case Study 4: LCA Approach for Solar Organic Photovoltaic Cells
Manufacturing
Index 613
Acknowledgments xvii
About the Authors xxi
CompanionWebsite xxiii
Nomenclature xxv
I INTRODUCTION 1
1 Introduction 3
1.1 Fundamentals of the Biorefinery Concept 3
1.1.1 Biorefinery Principles 3
1.1.2 Biorefinery Types and Development 4
1.2 Biorefinery Features and Nomenclature 5
1.3 Biorefinery Feedstock: Biomass 7
1.3.1 Chemical Nature of Biorefinery Feedstocks 8
1.3.2 Feedstock Characterization 10
1.4 Processes and Platforms 12
1.5 Biorefinery Products 15
1.6 Optimization of Preprocessing and Fractionation for Bio Based
Manufacturing 18
1.6.1 Background of Lignin 26
1.7 Electrochemistry Application in Biorefineries 31
1.8 Introduction to Energy and Water Systems 34
1.9 Evaluating Biorefinery Performances 36
1.9.1 Performance Indicators 36
1.9.2 Life Cycle Analysis 38
1.10 Chapters 38
1.11 Summary 38
References 39
II TOOLS 43
2 Economic Analysis 45
2.1 Introduction 45
2.2 General Economic Concepts and Terminology 46
2.2.1 Capital Cost and Battery Limits 46
2.2.2 Cost Index 46
2.2.3 Economies of Scale 47
2.2.4 Operating Cost 48
2.2.5 Cash Flows 49
2.2.6 Time Value of Money 49
2.2.7 Discounted Cash Flow Analysis and Net Present Value 50
2.2.8 Profitability Analysis 52
2.2.9 Learning Effect 53
2.3 Methodology 54
2.3.1 Capital Cost Estimation 54
2.3.2 Profitability Analysis 55
2.4 Cost Estimation and Correlation 55
2.4.1 Capital Cost 55
2.4.2 Operating Cost 58
2.5 Summary 59
2.6 Exercises 60
References 61
3 Heat Integration and Utility System Design 63
3.1 Introduction 63
3.2 Process Integration 64
3.3 Analysis of Heat Exchanger Network Using Pinch Technology 65
3.3.1 Data Extraction 66
3.3.2 Construction of Temperature-Enthalpy Profiles 69
3.3.3 Application of the Graphical Approach for Energy Recovery 76
3.4 Utility System 83
3.4.1 Components in Utility System 83
3.5 Conceptual Design of Heat Recovery System for Cogeneration 88
3.5.1 Conventional Approach 88
3.5.2 Heuristic Based Approach 88
3.6 Summary 91
References 91
4 Life Cycle Assessment 93
4.1 Life Cycle Thinking 93
4.2 Policy Context 96
4.3 Life Cycle Assessment (LCA) 96
4.4 LCA: Goal and Scope Definition 100
4.5 LCA: Inventory Analysis 104
4.6 LCA: Impact Assessment 111
4.6.1 Global Warming Potential 114
4.6.2 Land Use 115
4.6.3 Resource Use 119
4.6.4 Ozone Layer Depletion 121
4.6.5 Acidification Potential 123
4.6.6 Photochemical Oxidant Creation Potential 126
4.6.7 Aquatic Ecotoxicity 127
4.6.8 Eutrophication Potential 127
4.6.9 Biodiversity 128
4.7 LCA: Interpretation 128
4.7.1 Stand-Alone LCA 128
4.7.2 Accounting LCA 129
4.7.3 Change Oriented LCA 129
4.7.4 Allocation Method 129
4.8 LCIA Methods 130
4.9 Future R&D Needs 145
References 145
5 Data Uncertainty and Multicriteria Analyses 147
5.1 Data Uncertainty Analysis 147
5.1.1 Dominance Analysis 148
5.1.2 Contribution Analysis 149
5.1.3 Scenario Analysis 151
5.1.4 Sensitivity Analysis 153
5.1.5 Monte Carlo Simulation 154
5.2 Multicriteria Analysis 159
5.2.1 Economic Value and Environmental Impact Analysis of Biorefinery
Systems 160
5.2.2 Socioeconomic Analysis 163
5.3 Summary 165
References 165
6 Value Analysis 167
6.1 Value on Processing (VOP) and Cost of Production (COP) of Process
Network Streams 168
6.2 Value Analysis Heuristics 172
6.2.1 Discounted Cash Flow Analysis 173
6.3 Stream Economic Profile 175
6.4 Concept of Boundary and Evaluation of Economic Margin of a Process
Network 175
6.5 Stream Profitability Analysis 176
6.5.1 Value Analysis to Determine Necessary and Sufficient Condition for
Streams to be Profitable or Nonprofitable 181
6.6 Summary 187
References 187
7 Combined Economic Value and Environmental Impact (EVEI) Analysis 189
7.1 Introduction 189
7.2 Equivalency Between Economic and Environmental Impact Concepts 190
7.3 Evaluation of Streams 196
7.4 Environmental Impact Profile 200
7.5 Product Economic Value and Environmental Impact (EVEI) Profile 201
7.6 Summary 204
References 205
8 Optimization 207
8.1 Introduction 207
8.2 Linear Optimization 208
8.2.1 Step 1: Rewriting in Standard LP Format 210
8.2.2 Step 2: Initializing the Simplex Method 211
8.2.3 Step 3: Obtaining an Initial Basic Solution 212
8.2.4 Step 4: Determining Simplex Directions 212
8.2.5 Step 5: Determining the Maximum Step Size by the Minimum Ratio Rule
213
8.2.6 Step 6: Updating the Basic Variables 214
8.3 Nonlinear Optimization 218
8.3.1 Gradient Based Methods 219
8.3.2 Generalized Reduced Gradient (GRG) Algorithm 226
8.4 Mixed Integer Linear or Nonlinear Optimization 239
8.4.1 Branch and Bound Method 240
8.5 Stochastic Method 243
8.5.1 Genetic Algorithm (GA) 244
8.5.2 Non-dominated Sorting Genetic Algorithm (NSGA) Optimization 246
8.5.3 GA in MATLAB 248
8.6 Summary 248
References 248
III PROCESS SYNTHESIS AND DESIGN 251
9 Generic Reactors: Thermochemical Processing of Biomass 253
9.1 Introduction 253
9.2 General Features of Thermochemical Conversion Processes 254
9.3 Combustion 257
9.4 Gasification 258
9.4.1 The Process 258
9.4.2 Types of Gasifier 260
9.4.3 Design Considerations 260
9.5 Pyrolysis 262
9.5.1 What is Bio-Oil? 262
9.5.2 How Is Bio-Oil Obtained from Biomass? 264
9.5.3 How Fast Pyrolysis Works 265
9.6 Summary 270
Exercises 270
References 270
10 Reaction Thermodynamics 271
10.1 Introduction 271
10.2 Fundamentals of Design Calculation 272
10.2.1 Heat of Combustion 272
10.2.2 Higher and Lower Heating Values 276
10.2.3 Adiabatic Flame Temperature 278
10.2.4 Theoretical Air-to-Fuel Ratio 279
10.2.5 Cold Gas Efficiency 280
10.2.6 Hot Gas Efficiency 281
10.2.7 Equivalence Ratio 281
10.2.8 Carbon Conversion 282
10.2.9 Heat of Reaction 282
10.3 Process Design: Synthesis and Modeling 282
10.3.1 Combustion Model 282
10.3.2 Gasification Model 283
10.3.3 Pyrolysis Model 289
10.4 Summary 291
Exercises 291
References 292
11 Reaction and Separation Process Synthesis: Chemical Production from
Biomass 295
11.1 Chemicals from Biomass: An Overview 296
11.2 Bioreactor and Kinetics 297
11.2.1 An Example of Lactic Acid Production 299
11.2.2 An Example of Succinic Acid Production 304
11.2.3 Heat Transfer Strategies for Reactors 308
11.2.4 An Example of Ethylene Production 309
11.2.5 An Example of Catalytic Fast Pyrolysis 311
11.3 Controlled Acid Hydrolysis Reactions 318
11.4 Advanced Separation and Reactive Separation 327
11.4.1 Membrane Based Separations 327
11.4.2 Membrane Filtration 330
11.4.3 Electrodialysis 333
11.4.4 Ion Exchange 334
11.4.5 Integrated Processes 338
11.4.6 Reactive Extraction 341
11.4.7 Reactive Distillation 352
11.4.8 Crystallization 354
11.4.9 Precipitation 360
11.5 Guidelines for Integrated Biorefinery Design 360
11.5.1 An Example of Levulinic Acid Production: The Biofine Process 365
11.6 Summary 368
References 370
12 Polymer Processes 373
12.1 Polymer Concepts 374
12.1.1 Polymer Classification 375
12.1.2 Polymer Properties 376
12.1.3 From Petrochemical Based Polymers to Biopolymers 379
12.2 Modified Natural Biopolymers 385
12.2.1 Starch Polymers 385
12.2.2 Cellulose Polymers 389
12.2.3 Natural Fiber and Lignin Composites 389
12.3 Modeling of Polymerization Reaction Kinetics 391
12.3.1 Chain-Growth or Addition Polymerization 392
12.3.2 Step-Growth Polymerization 396
12.3.3 Copolymerization 398
12.4 Reactor Design for Biomass Based Monomers and Biopolymers 400
12.4.1 Plug Flow Reactor (PFR) Design for Reaction in Gaseous Phase 400
12.4.2 Bioreactor Design for Biopolymer Production - An Example of
Polyhydroxyalkanoates 402
12.4.3 Catalytic Reactor Design 403
12.4.4 Energy Transfer Models of Reactors 412
12.5 Synthesis of Unit Operations Combining Reaction and Separation
Functionalities 416
12.5.1 Reactive Distillation Column 416
12.5.2 An Example of a Novel Reactor Arrangement 418
12.6 Integrated Biopolymer Production in Biorefineries 421
12.6.1 Polyesters 421
12.6.2 Polyurethanes 422
12.6.3 Polyamides 422
12.6.4 Polycarbonates 424
12.7 Summary 424
References 424
13 Separation Processes: Carbon Capture 425
13.1 Absorption 426
13.2 Absorption Process Flowsheet Synthesis 429
13.3 The RectisolTM Technology 431
13.3.1 Design and Operating Regions of RectisolTM Process 433
13.3.2 Energy Consumption of a RectisolTM Process 435
13.4 The SelexolTM Technology 446
13.4.1 SelexolTM Process Parametric Analysis 448
13.5 Adsorption Process 457
13.5.1 Kinetic Modeling of SMR Reactions 458
13.5.2 Adsorption Modeling of Carbon Dioxide 460
13.5.3 Sorption Enhanced Reaction (SER) Process Dynamic Modeling Framework
460
13.6 Chemical Looping Combustion 463
13.7 Low Temperature Separation 471
13.8 Summary 472
References 473
IV BIOREFINERY SYSTEMS 475
14 Bio-Oil Refining I: Fischer-Tropsch Liquid and Methanol Synthesis 477
14.1 Introduction 477
14.2 Bio-Oil Upgrading 478
14.2.1 Physical Upgrading 478
14.2.2 Chemical Upgrading 478
14.2.3 Biological Upgrading 480
14.3 Distributed and Centralized Bio-Oil Processing Concept 481
14.3.1 The Concept 481
14.3.2 The Economics of Local Distribution of Bio-Oil 482
14.3.3 The Economics of Importing Bio-Oil from Other Countries 483
14.4 Integrated Thermochemical Processing of Bio-Oil into Fuels 483
14.4.1 Synthetic Fuel Production 484
14.4.2 Methanol Production 485
14.5 Modeling, Integration and Analysis of Thermochemical Processes of
Bio-Oil 486
14.5.1 Flowsheet Synthesis and Modeling 486
14.5.2 Sensitivity Analysis 488
14.6 Summary 494
References 494
15 Bio-Oil Refining II: Novel Membrane Reactors 497
15.1 Bio-Oil Co-Processing in Crude Oil Refinery 497
15.2 Mixed Ionic Electronic Conducting (MIEC) Membrane for Hydrogen
Production and Bio-Oil Hydrotreating and Hydrocracking 499
15.3 Bio-Oil Hydrotreating and Hydrocracking Reaction Mechanisms and a MIEC
Membrane Reactor Based Bio-Oil Upgrader Process Flowsheet 502
15.4 A Coursework Problem 510
15.5 Summary 513
References 514
16 Fuel Cells and Other Renewables 515
16.1 Biomass Integrated Gasification Fuel Cell (BGFC) System Modeling for
Design, Integration and Analysis 517
16.2 Simulation of Integrated BGFC Flowsheets 520
16.3 Heat Integration of BGFC Flowsheets 528
16.4 Analysis of Processing Chains in BGFC Flowsheets 529
16.5 SOFC Gibbs Free Energy Minimization Modeling 532
16.6 Design of SOFC Based Micro-CHP Systems 536
16.7 Fuel Cell and SOFC Design Parameterization Suitable for Spreadsheet
Implementation 537
16.7.1 Mass Balance 539
16.7.2 Electrochemical Descriptions 540
16.7.3 An air Blower Power Consumption 542
16.7.4 Combustor Modeling 543
16.7.5 Energy Balance 543
16.8 Summary 546
References 546
17 Algae Biorefineries 547
17.1 Algae Cultivation 548
17.1.1 Open Pond Cultivation 548
17.1.2 Photobioreactors (PBRs) 556
17.2 Algae Harvesting and Oil Extraction 562
17.2.1 Harvesting 562
17.2.2 Extraction 570
17.3 Algae Biodiesel Production 570
17.3.1 Biodiesel Process 570
17.3.2 Heterogeneous Catalysts for Transesterification 572
17.4 Algae Biorefinery Integration 572
17.5 Life Cycle Assessment of Algae Biorefineries 575
17.6 Summary 579
References 579
18 Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling:
Example of Biodiesel 581
18.1 Intrinsic Kinetic Modeling 582
18.1.1 Elementary Reaction Mechanism and Intrinsic Kinetic Modeling of the
Biodiesel Production System 582
18.1.2 Solution Strategy for the Rate Equations Resulting from the
Elementary Reaction Mechanism 590
18.1.3 Correlation between Concentration and Activity of Species Using the
UNIQUAC Contribution Method 591
18.1.4 An Example of EXCEL Spreadsheet Based UNIQUAC Calculation for a
Biodiesel Production System is Shown in Detail for Implementation in Online
Resource Material, Chapter 18 - Additional Exercises and Examples 592
18.1.5 Intrinsic Kinetic Modeling Framework 592
18.2 Diffusion Modeling 595
18.3 Multi-scale Mass Transfer Modeling 598
18.3.1 Dimensionless Physical Parameter Groups 606
18.4 Summary 612
References 612
V ONLINE RESOURCES
Web Chapter 1: Waste and Emission Minimization
Web Chapter 2: Energy Storage and Control Systems
Web Chapter 3: Water Reuse, Footprint and Optimization Analysis
Case Study 1: Biomass CHP Plant Design Problem - LCA and Cost Analysis
Case Study 2: Comparison between Epoxy Resin Productions from Algal or Soya
Oil - An LCA Based Problem Solving Approach
Case Study 3: Waste Water Sludge Based CHP and Agricultural Application
System - An LCA Based Problem Solving Approach
Case Study 4: LCA Approach for Solar Organic Photovoltaic Cells
Manufacturing
Index 613
Preface xiii
Acknowledgments xvii
About the Authors xxi
CompanionWebsite xxiii
Nomenclature xxv
I INTRODUCTION 1
1 Introduction 3
1.1 Fundamentals of the Biorefinery Concept 3
1.1.1 Biorefinery Principles 3
1.1.2 Biorefinery Types and Development 4
1.2 Biorefinery Features and Nomenclature 5
1.3 Biorefinery Feedstock: Biomass 7
1.3.1 Chemical Nature of Biorefinery Feedstocks 8
1.3.2 Feedstock Characterization 10
1.4 Processes and Platforms 12
1.5 Biorefinery Products 15
1.6 Optimization of Preprocessing and Fractionation for Bio Based
Manufacturing 18
1.6.1 Background of Lignin 26
1.7 Electrochemistry Application in Biorefineries 31
1.8 Introduction to Energy and Water Systems 34
1.9 Evaluating Biorefinery Performances 36
1.9.1 Performance Indicators 36
1.9.2 Life Cycle Analysis 38
1.10 Chapters 38
1.11 Summary 38
References 39
II TOOLS 43
2 Economic Analysis 45
2.1 Introduction 45
2.2 General Economic Concepts and Terminology 46
2.2.1 Capital Cost and Battery Limits 46
2.2.2 Cost Index 46
2.2.3 Economies of Scale 47
2.2.4 Operating Cost 48
2.2.5 Cash Flows 49
2.2.6 Time Value of Money 49
2.2.7 Discounted Cash Flow Analysis and Net Present Value 50
2.2.8 Profitability Analysis 52
2.2.9 Learning Effect 53
2.3 Methodology 54
2.3.1 Capital Cost Estimation 54
2.3.2 Profitability Analysis 55
2.4 Cost Estimation and Correlation 55
2.4.1 Capital Cost 55
2.4.2 Operating Cost 58
2.5 Summary 59
2.6 Exercises 60
References 61
3 Heat Integration and Utility System Design 63
3.1 Introduction 63
3.2 Process Integration 64
3.3 Analysis of Heat Exchanger Network Using Pinch Technology 65
3.3.1 Data Extraction 66
3.3.2 Construction of Temperature-Enthalpy Profiles 69
3.3.3 Application of the Graphical Approach for Energy Recovery 76
3.4 Utility System 83
3.4.1 Components in Utility System 83
3.5 Conceptual Design of Heat Recovery System for Cogeneration 88
3.5.1 Conventional Approach 88
3.5.2 Heuristic Based Approach 88
3.6 Summary 91
References 91
4 Life Cycle Assessment 93
4.1 Life Cycle Thinking 93
4.2 Policy Context 96
4.3 Life Cycle Assessment (LCA) 96
4.4 LCA: Goal and Scope Definition 100
4.5 LCA: Inventory Analysis 104
4.6 LCA: Impact Assessment 111
4.6.1 Global Warming Potential 114
4.6.2 Land Use 115
4.6.3 Resource Use 119
4.6.4 Ozone Layer Depletion 121
4.6.5 Acidification Potential 123
4.6.6 Photochemical Oxidant Creation Potential 126
4.6.7 Aquatic Ecotoxicity 127
4.6.8 Eutrophication Potential 127
4.6.9 Biodiversity 128
4.7 LCA: Interpretation 128
4.7.1 Stand-Alone LCA 128
4.7.2 Accounting LCA 129
4.7.3 Change Oriented LCA 129
4.7.4 Allocation Method 129
4.8 LCIA Methods 130
4.9 Future R&D Needs 145
References 145
5 Data Uncertainty and Multicriteria Analyses 147
5.1 Data Uncertainty Analysis 147
5.1.1 Dominance Analysis 148
5.1.2 Contribution Analysis 149
5.1.3 Scenario Analysis 151
5.1.4 Sensitivity Analysis 153
5.1.5 Monte Carlo Simulation 154
5.2 Multicriteria Analysis 159
5.2.1 Economic Value and Environmental Impact Analysis of Biorefinery
Systems 160
5.2.2 Socioeconomic Analysis 163
5.3 Summary 165
References 165
6 Value Analysis 167
6.1 Value on Processing (VOP) and Cost of Production (COP) of Process
Network Streams 168
6.2 Value Analysis Heuristics 172
6.2.1 Discounted Cash Flow Analysis 173
6.3 Stream Economic Profile 175
6.4 Concept of Boundary and Evaluation of Economic Margin of a Process
Network 175
6.5 Stream Profitability Analysis 176
6.5.1 Value Analysis to Determine Necessary and Sufficient Condition for
Streams to be Profitable or Nonprofitable 181
6.6 Summary 187
References 187
7 Combined Economic Value and Environmental Impact (EVEI) Analysis 189
7.1 Introduction 189
7.2 Equivalency Between Economic and Environmental Impact Concepts 190
7.3 Evaluation of Streams 196
7.4 Environmental Impact Profile 200
7.5 Product Economic Value and Environmental Impact (EVEI) Profile 201
7.6 Summary 204
References 205
8 Optimization 207
8.1 Introduction 207
8.2 Linear Optimization 208
8.2.1 Step 1: Rewriting in Standard LP Format 210
8.2.2 Step 2: Initializing the Simplex Method 211
8.2.3 Step 3: Obtaining an Initial Basic Solution 212
8.2.4 Step 4: Determining Simplex Directions 212
8.2.5 Step 5: Determining the Maximum Step Size by the Minimum Ratio Rule
213
8.2.6 Step 6: Updating the Basic Variables 214
8.3 Nonlinear Optimization 218
8.3.1 Gradient Based Methods 219
8.3.2 Generalized Reduced Gradient (GRG) Algorithm 226
8.4 Mixed Integer Linear or Nonlinear Optimization 239
8.4.1 Branch and Bound Method 240
8.5 Stochastic Method 243
8.5.1 Genetic Algorithm (GA) 244
8.5.2 Non-dominated Sorting Genetic Algorithm (NSGA) Optimization 246
8.5.3 GA in MATLAB 248
8.6 Summary 248
References 248
III PROCESS SYNTHESIS AND DESIGN 251
9 Generic Reactors: Thermochemical Processing of Biomass 253
9.1 Introduction 253
9.2 General Features of Thermochemical Conversion Processes 254
9.3 Combustion 257
9.4 Gasification 258
9.4.1 The Process 258
9.4.2 Types of Gasifier 260
9.4.3 Design Considerations 260
9.5 Pyrolysis 262
9.5.1 What is Bio-Oil? 262
9.5.2 How Is Bio-Oil Obtained from Biomass? 264
9.5.3 How Fast Pyrolysis Works 265
9.6 Summary 270
Exercises 270
References 270
10 Reaction Thermodynamics 271
10.1 Introduction 271
10.2 Fundamentals of Design Calculation 272
10.2.1 Heat of Combustion 272
10.2.2 Higher and Lower Heating Values 276
10.2.3 Adiabatic Flame Temperature 278
10.2.4 Theoretical Air-to-Fuel Ratio 279
10.2.5 Cold Gas Efficiency 280
10.2.6 Hot Gas Efficiency 281
10.2.7 Equivalence Ratio 281
10.2.8 Carbon Conversion 282
10.2.9 Heat of Reaction 282
10.3 Process Design: Synthesis and Modeling 282
10.3.1 Combustion Model 282
10.3.2 Gasification Model 283
10.3.3 Pyrolysis Model 289
10.4 Summary 291
Exercises 291
References 292
11 Reaction and Separation Process Synthesis: Chemical Production from
Biomass 295
11.1 Chemicals from Biomass: An Overview 296
11.2 Bioreactor and Kinetics 297
11.2.1 An Example of Lactic Acid Production 299
11.2.2 An Example of Succinic Acid Production 304
11.2.3 Heat Transfer Strategies for Reactors 308
11.2.4 An Example of Ethylene Production 309
11.2.5 An Example of Catalytic Fast Pyrolysis 311
11.3 Controlled Acid Hydrolysis Reactions 318
11.4 Advanced Separation and Reactive Separation 327
11.4.1 Membrane Based Separations 327
11.4.2 Membrane Filtration 330
11.4.3 Electrodialysis 333
11.4.4 Ion Exchange 334
11.4.5 Integrated Processes 338
11.4.6 Reactive Extraction 341
11.4.7 Reactive Distillation 352
11.4.8 Crystallization 354
11.4.9 Precipitation 360
11.5 Guidelines for Integrated Biorefinery Design 360
11.5.1 An Example of Levulinic Acid Production: The Biofine Process 365
11.6 Summary 368
References 370
12 Polymer Processes 373
12.1 Polymer Concepts 374
12.1.1 Polymer Classification 375
12.1.2 Polymer Properties 376
12.1.3 From Petrochemical Based Polymers to Biopolymers 379
12.2 Modified Natural Biopolymers 385
12.2.1 Starch Polymers 385
12.2.2 Cellulose Polymers 389
12.2.3 Natural Fiber and Lignin Composites 389
12.3 Modeling of Polymerization Reaction Kinetics 391
12.3.1 Chain-Growth or Addition Polymerization 392
12.3.2 Step-Growth Polymerization 396
12.3.3 Copolymerization 398
12.4 Reactor Design for Biomass Based Monomers and Biopolymers 400
12.4.1 Plug Flow Reactor (PFR) Design for Reaction in Gaseous Phase 400
12.4.2 Bioreactor Design for Biopolymer Production - An Example of
Polyhydroxyalkanoates 402
12.4.3 Catalytic Reactor Design 403
12.4.4 Energy Transfer Models of Reactors 412
12.5 Synthesis of Unit Operations Combining Reaction and Separation
Functionalities 416
12.5.1 Reactive Distillation Column 416
12.5.2 An Example of a Novel Reactor Arrangement 418
12.6 Integrated Biopolymer Production in Biorefineries 421
12.6.1 Polyesters 421
12.6.2 Polyurethanes 422
12.6.3 Polyamides 422
12.6.4 Polycarbonates 424
12.7 Summary 424
References 424
13 Separation Processes: Carbon Capture 425
13.1 Absorption 426
13.2 Absorption Process Flowsheet Synthesis 429
13.3 The RectisolTM Technology 431
13.3.1 Design and Operating Regions of RectisolTM Process 433
13.3.2 Energy Consumption of a RectisolTM Process 435
13.4 The SelexolTM Technology 446
13.4.1 SelexolTM Process Parametric Analysis 448
13.5 Adsorption Process 457
13.5.1 Kinetic Modeling of SMR Reactions 458
13.5.2 Adsorption Modeling of Carbon Dioxide 460
13.5.3 Sorption Enhanced Reaction (SER) Process Dynamic Modeling Framework
460
13.6 Chemical Looping Combustion 463
13.7 Low Temperature Separation 471
13.8 Summary 472
References 473
IV BIOREFINERY SYSTEMS 475
14 Bio-Oil Refining I: Fischer-Tropsch Liquid and Methanol Synthesis 477
14.1 Introduction 477
14.2 Bio-Oil Upgrading 478
14.2.1 Physical Upgrading 478
14.2.2 Chemical Upgrading 478
14.2.3 Biological Upgrading 480
14.3 Distributed and Centralized Bio-Oil Processing Concept 481
14.3.1 The Concept 481
14.3.2 The Economics of Local Distribution of Bio-Oil 482
14.3.3 The Economics of Importing Bio-Oil from Other Countries 483
14.4 Integrated Thermochemical Processing of Bio-Oil into Fuels 483
14.4.1 Synthetic Fuel Production 484
14.4.2 Methanol Production 485
14.5 Modeling, Integration and Analysis of Thermochemical Processes of
Bio-Oil 486
14.5.1 Flowsheet Synthesis and Modeling 486
14.5.2 Sensitivity Analysis 488
14.6 Summary 494
References 494
15 Bio-Oil Refining II: Novel Membrane Reactors 497
15.1 Bio-Oil Co-Processing in Crude Oil Refinery 497
15.2 Mixed Ionic Electronic Conducting (MIEC) Membrane for Hydrogen
Production and Bio-Oil Hydrotreating and Hydrocracking 499
15.3 Bio-Oil Hydrotreating and Hydrocracking Reaction Mechanisms and a MIEC
Membrane Reactor Based Bio-Oil Upgrader Process Flowsheet 502
15.4 A Coursework Problem 510
15.5 Summary 513
References 514
16 Fuel Cells and Other Renewables 515
16.1 Biomass Integrated Gasification Fuel Cell (BGFC) System Modeling for
Design, Integration and Analysis 517
16.2 Simulation of Integrated BGFC Flowsheets 520
16.3 Heat Integration of BGFC Flowsheets 528
16.4 Analysis of Processing Chains in BGFC Flowsheets 529
16.5 SOFC Gibbs Free Energy Minimization Modeling 532
16.6 Design of SOFC Based Micro-CHP Systems 536
16.7 Fuel Cell and SOFC Design Parameterization Suitable for Spreadsheet
Implementation 537
16.7.1 Mass Balance 539
16.7.2 Electrochemical Descriptions 540
16.7.3 An air Blower Power Consumption 542
16.7.4 Combustor Modeling 543
16.7.5 Energy Balance 543
16.8 Summary 546
References 546
17 Algae Biorefineries 547
17.1 Algae Cultivation 548
17.1.1 Open Pond Cultivation 548
17.1.2 Photobioreactors (PBRs) 556
17.2 Algae Harvesting and Oil Extraction 562
17.2.1 Harvesting 562
17.2.2 Extraction 570
17.3 Algae Biodiesel Production 570
17.3.1 Biodiesel Process 570
17.3.2 Heterogeneous Catalysts for Transesterification 572
17.4 Algae Biorefinery Integration 572
17.5 Life Cycle Assessment of Algae Biorefineries 575
17.6 Summary 579
References 579
18 Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling:
Example of Biodiesel 581
18.1 Intrinsic Kinetic Modeling 582
18.1.1 Elementary Reaction Mechanism and Intrinsic Kinetic Modeling of the
Biodiesel Production System 582
18.1.2 Solution Strategy for the Rate Equations Resulting from the
Elementary Reaction Mechanism 590
18.1.3 Correlation between Concentration and Activity of Species Using the
UNIQUAC Contribution Method 591
18.1.4 An Example of EXCEL Spreadsheet Based UNIQUAC Calculation for a
Biodiesel Production System is Shown in Detail for Implementation in Online
Resource Material, Chapter 18 - Additional Exercises and Examples 592
18.1.5 Intrinsic Kinetic Modeling Framework 592
18.2 Diffusion Modeling 595
18.3 Multi-scale Mass Transfer Modeling 598
18.3.1 Dimensionless Physical Parameter Groups 606
18.4 Summary 612
References 612
V ONLINE RESOURCES
Web Chapter 1: Waste and Emission Minimization
Web Chapter 2: Energy Storage and Control Systems
Web Chapter 3: Water Reuse, Footprint and Optimization Analysis
Case Study 1: Biomass CHP Plant Design Problem - LCA and Cost Analysis
Case Study 2: Comparison between Epoxy Resin Productions from Algal or Soya
Oil - An LCA Based Problem Solving Approach
Case Study 3: Waste Water Sludge Based CHP and Agricultural Application
System - An LCA Based Problem Solving Approach
Case Study 4: LCA Approach for Solar Organic Photovoltaic Cells
Manufacturing
Index 613
Acknowledgments xvii
About the Authors xxi
CompanionWebsite xxiii
Nomenclature xxv
I INTRODUCTION 1
1 Introduction 3
1.1 Fundamentals of the Biorefinery Concept 3
1.1.1 Biorefinery Principles 3
1.1.2 Biorefinery Types and Development 4
1.2 Biorefinery Features and Nomenclature 5
1.3 Biorefinery Feedstock: Biomass 7
1.3.1 Chemical Nature of Biorefinery Feedstocks 8
1.3.2 Feedstock Characterization 10
1.4 Processes and Platforms 12
1.5 Biorefinery Products 15
1.6 Optimization of Preprocessing and Fractionation for Bio Based
Manufacturing 18
1.6.1 Background of Lignin 26
1.7 Electrochemistry Application in Biorefineries 31
1.8 Introduction to Energy and Water Systems 34
1.9 Evaluating Biorefinery Performances 36
1.9.1 Performance Indicators 36
1.9.2 Life Cycle Analysis 38
1.10 Chapters 38
1.11 Summary 38
References 39
II TOOLS 43
2 Economic Analysis 45
2.1 Introduction 45
2.2 General Economic Concepts and Terminology 46
2.2.1 Capital Cost and Battery Limits 46
2.2.2 Cost Index 46
2.2.3 Economies of Scale 47
2.2.4 Operating Cost 48
2.2.5 Cash Flows 49
2.2.6 Time Value of Money 49
2.2.7 Discounted Cash Flow Analysis and Net Present Value 50
2.2.8 Profitability Analysis 52
2.2.9 Learning Effect 53
2.3 Methodology 54
2.3.1 Capital Cost Estimation 54
2.3.2 Profitability Analysis 55
2.4 Cost Estimation and Correlation 55
2.4.1 Capital Cost 55
2.4.2 Operating Cost 58
2.5 Summary 59
2.6 Exercises 60
References 61
3 Heat Integration and Utility System Design 63
3.1 Introduction 63
3.2 Process Integration 64
3.3 Analysis of Heat Exchanger Network Using Pinch Technology 65
3.3.1 Data Extraction 66
3.3.2 Construction of Temperature-Enthalpy Profiles 69
3.3.3 Application of the Graphical Approach for Energy Recovery 76
3.4 Utility System 83
3.4.1 Components in Utility System 83
3.5 Conceptual Design of Heat Recovery System for Cogeneration 88
3.5.1 Conventional Approach 88
3.5.2 Heuristic Based Approach 88
3.6 Summary 91
References 91
4 Life Cycle Assessment 93
4.1 Life Cycle Thinking 93
4.2 Policy Context 96
4.3 Life Cycle Assessment (LCA) 96
4.4 LCA: Goal and Scope Definition 100
4.5 LCA: Inventory Analysis 104
4.6 LCA: Impact Assessment 111
4.6.1 Global Warming Potential 114
4.6.2 Land Use 115
4.6.3 Resource Use 119
4.6.4 Ozone Layer Depletion 121
4.6.5 Acidification Potential 123
4.6.6 Photochemical Oxidant Creation Potential 126
4.6.7 Aquatic Ecotoxicity 127
4.6.8 Eutrophication Potential 127
4.6.9 Biodiversity 128
4.7 LCA: Interpretation 128
4.7.1 Stand-Alone LCA 128
4.7.2 Accounting LCA 129
4.7.3 Change Oriented LCA 129
4.7.4 Allocation Method 129
4.8 LCIA Methods 130
4.9 Future R&D Needs 145
References 145
5 Data Uncertainty and Multicriteria Analyses 147
5.1 Data Uncertainty Analysis 147
5.1.1 Dominance Analysis 148
5.1.2 Contribution Analysis 149
5.1.3 Scenario Analysis 151
5.1.4 Sensitivity Analysis 153
5.1.5 Monte Carlo Simulation 154
5.2 Multicriteria Analysis 159
5.2.1 Economic Value and Environmental Impact Analysis of Biorefinery
Systems 160
5.2.2 Socioeconomic Analysis 163
5.3 Summary 165
References 165
6 Value Analysis 167
6.1 Value on Processing (VOP) and Cost of Production (COP) of Process
Network Streams 168
6.2 Value Analysis Heuristics 172
6.2.1 Discounted Cash Flow Analysis 173
6.3 Stream Economic Profile 175
6.4 Concept of Boundary and Evaluation of Economic Margin of a Process
Network 175
6.5 Stream Profitability Analysis 176
6.5.1 Value Analysis to Determine Necessary and Sufficient Condition for
Streams to be Profitable or Nonprofitable 181
6.6 Summary 187
References 187
7 Combined Economic Value and Environmental Impact (EVEI) Analysis 189
7.1 Introduction 189
7.2 Equivalency Between Economic and Environmental Impact Concepts 190
7.3 Evaluation of Streams 196
7.4 Environmental Impact Profile 200
7.5 Product Economic Value and Environmental Impact (EVEI) Profile 201
7.6 Summary 204
References 205
8 Optimization 207
8.1 Introduction 207
8.2 Linear Optimization 208
8.2.1 Step 1: Rewriting in Standard LP Format 210
8.2.2 Step 2: Initializing the Simplex Method 211
8.2.3 Step 3: Obtaining an Initial Basic Solution 212
8.2.4 Step 4: Determining Simplex Directions 212
8.2.5 Step 5: Determining the Maximum Step Size by the Minimum Ratio Rule
213
8.2.6 Step 6: Updating the Basic Variables 214
8.3 Nonlinear Optimization 218
8.3.1 Gradient Based Methods 219
8.3.2 Generalized Reduced Gradient (GRG) Algorithm 226
8.4 Mixed Integer Linear or Nonlinear Optimization 239
8.4.1 Branch and Bound Method 240
8.5 Stochastic Method 243
8.5.1 Genetic Algorithm (GA) 244
8.5.2 Non-dominated Sorting Genetic Algorithm (NSGA) Optimization 246
8.5.3 GA in MATLAB 248
8.6 Summary 248
References 248
III PROCESS SYNTHESIS AND DESIGN 251
9 Generic Reactors: Thermochemical Processing of Biomass 253
9.1 Introduction 253
9.2 General Features of Thermochemical Conversion Processes 254
9.3 Combustion 257
9.4 Gasification 258
9.4.1 The Process 258
9.4.2 Types of Gasifier 260
9.4.3 Design Considerations 260
9.5 Pyrolysis 262
9.5.1 What is Bio-Oil? 262
9.5.2 How Is Bio-Oil Obtained from Biomass? 264
9.5.3 How Fast Pyrolysis Works 265
9.6 Summary 270
Exercises 270
References 270
10 Reaction Thermodynamics 271
10.1 Introduction 271
10.2 Fundamentals of Design Calculation 272
10.2.1 Heat of Combustion 272
10.2.2 Higher and Lower Heating Values 276
10.2.3 Adiabatic Flame Temperature 278
10.2.4 Theoretical Air-to-Fuel Ratio 279
10.2.5 Cold Gas Efficiency 280
10.2.6 Hot Gas Efficiency 281
10.2.7 Equivalence Ratio 281
10.2.8 Carbon Conversion 282
10.2.9 Heat of Reaction 282
10.3 Process Design: Synthesis and Modeling 282
10.3.1 Combustion Model 282
10.3.2 Gasification Model 283
10.3.3 Pyrolysis Model 289
10.4 Summary 291
Exercises 291
References 292
11 Reaction and Separation Process Synthesis: Chemical Production from
Biomass 295
11.1 Chemicals from Biomass: An Overview 296
11.2 Bioreactor and Kinetics 297
11.2.1 An Example of Lactic Acid Production 299
11.2.2 An Example of Succinic Acid Production 304
11.2.3 Heat Transfer Strategies for Reactors 308
11.2.4 An Example of Ethylene Production 309
11.2.5 An Example of Catalytic Fast Pyrolysis 311
11.3 Controlled Acid Hydrolysis Reactions 318
11.4 Advanced Separation and Reactive Separation 327
11.4.1 Membrane Based Separations 327
11.4.2 Membrane Filtration 330
11.4.3 Electrodialysis 333
11.4.4 Ion Exchange 334
11.4.5 Integrated Processes 338
11.4.6 Reactive Extraction 341
11.4.7 Reactive Distillation 352
11.4.8 Crystallization 354
11.4.9 Precipitation 360
11.5 Guidelines for Integrated Biorefinery Design 360
11.5.1 An Example of Levulinic Acid Production: The Biofine Process 365
11.6 Summary 368
References 370
12 Polymer Processes 373
12.1 Polymer Concepts 374
12.1.1 Polymer Classification 375
12.1.2 Polymer Properties 376
12.1.3 From Petrochemical Based Polymers to Biopolymers 379
12.2 Modified Natural Biopolymers 385
12.2.1 Starch Polymers 385
12.2.2 Cellulose Polymers 389
12.2.3 Natural Fiber and Lignin Composites 389
12.3 Modeling of Polymerization Reaction Kinetics 391
12.3.1 Chain-Growth or Addition Polymerization 392
12.3.2 Step-Growth Polymerization 396
12.3.3 Copolymerization 398
12.4 Reactor Design for Biomass Based Monomers and Biopolymers 400
12.4.1 Plug Flow Reactor (PFR) Design for Reaction in Gaseous Phase 400
12.4.2 Bioreactor Design for Biopolymer Production - An Example of
Polyhydroxyalkanoates 402
12.4.3 Catalytic Reactor Design 403
12.4.4 Energy Transfer Models of Reactors 412
12.5 Synthesis of Unit Operations Combining Reaction and Separation
Functionalities 416
12.5.1 Reactive Distillation Column 416
12.5.2 An Example of a Novel Reactor Arrangement 418
12.6 Integrated Biopolymer Production in Biorefineries 421
12.6.1 Polyesters 421
12.6.2 Polyurethanes 422
12.6.3 Polyamides 422
12.6.4 Polycarbonates 424
12.7 Summary 424
References 424
13 Separation Processes: Carbon Capture 425
13.1 Absorption 426
13.2 Absorption Process Flowsheet Synthesis 429
13.3 The RectisolTM Technology 431
13.3.1 Design and Operating Regions of RectisolTM Process 433
13.3.2 Energy Consumption of a RectisolTM Process 435
13.4 The SelexolTM Technology 446
13.4.1 SelexolTM Process Parametric Analysis 448
13.5 Adsorption Process 457
13.5.1 Kinetic Modeling of SMR Reactions 458
13.5.2 Adsorption Modeling of Carbon Dioxide 460
13.5.3 Sorption Enhanced Reaction (SER) Process Dynamic Modeling Framework
460
13.6 Chemical Looping Combustion 463
13.7 Low Temperature Separation 471
13.8 Summary 472
References 473
IV BIOREFINERY SYSTEMS 475
14 Bio-Oil Refining I: Fischer-Tropsch Liquid and Methanol Synthesis 477
14.1 Introduction 477
14.2 Bio-Oil Upgrading 478
14.2.1 Physical Upgrading 478
14.2.2 Chemical Upgrading 478
14.2.3 Biological Upgrading 480
14.3 Distributed and Centralized Bio-Oil Processing Concept 481
14.3.1 The Concept 481
14.3.2 The Economics of Local Distribution of Bio-Oil 482
14.3.3 The Economics of Importing Bio-Oil from Other Countries 483
14.4 Integrated Thermochemical Processing of Bio-Oil into Fuels 483
14.4.1 Synthetic Fuel Production 484
14.4.2 Methanol Production 485
14.5 Modeling, Integration and Analysis of Thermochemical Processes of
Bio-Oil 486
14.5.1 Flowsheet Synthesis and Modeling 486
14.5.2 Sensitivity Analysis 488
14.6 Summary 494
References 494
15 Bio-Oil Refining II: Novel Membrane Reactors 497
15.1 Bio-Oil Co-Processing in Crude Oil Refinery 497
15.2 Mixed Ionic Electronic Conducting (MIEC) Membrane for Hydrogen
Production and Bio-Oil Hydrotreating and Hydrocracking 499
15.3 Bio-Oil Hydrotreating and Hydrocracking Reaction Mechanisms and a MIEC
Membrane Reactor Based Bio-Oil Upgrader Process Flowsheet 502
15.4 A Coursework Problem 510
15.5 Summary 513
References 514
16 Fuel Cells and Other Renewables 515
16.1 Biomass Integrated Gasification Fuel Cell (BGFC) System Modeling for
Design, Integration and Analysis 517
16.2 Simulation of Integrated BGFC Flowsheets 520
16.3 Heat Integration of BGFC Flowsheets 528
16.4 Analysis of Processing Chains in BGFC Flowsheets 529
16.5 SOFC Gibbs Free Energy Minimization Modeling 532
16.6 Design of SOFC Based Micro-CHP Systems 536
16.7 Fuel Cell and SOFC Design Parameterization Suitable for Spreadsheet
Implementation 537
16.7.1 Mass Balance 539
16.7.2 Electrochemical Descriptions 540
16.7.3 An air Blower Power Consumption 542
16.7.4 Combustor Modeling 543
16.7.5 Energy Balance 543
16.8 Summary 546
References 546
17 Algae Biorefineries 547
17.1 Algae Cultivation 548
17.1.1 Open Pond Cultivation 548
17.1.2 Photobioreactors (PBRs) 556
17.2 Algae Harvesting and Oil Extraction 562
17.2.1 Harvesting 562
17.2.2 Extraction 570
17.3 Algae Biodiesel Production 570
17.3.1 Biodiesel Process 570
17.3.2 Heterogeneous Catalysts for Transesterification 572
17.4 Algae Biorefinery Integration 572
17.5 Life Cycle Assessment of Algae Biorefineries 575
17.6 Summary 579
References 579
18 Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling:
Example of Biodiesel 581
18.1 Intrinsic Kinetic Modeling 582
18.1.1 Elementary Reaction Mechanism and Intrinsic Kinetic Modeling of the
Biodiesel Production System 582
18.1.2 Solution Strategy for the Rate Equations Resulting from the
Elementary Reaction Mechanism 590
18.1.3 Correlation between Concentration and Activity of Species Using the
UNIQUAC Contribution Method 591
18.1.4 An Example of EXCEL Spreadsheet Based UNIQUAC Calculation for a
Biodiesel Production System is Shown in Detail for Implementation in Online
Resource Material, Chapter 18 - Additional Exercises and Examples 592
18.1.5 Intrinsic Kinetic Modeling Framework 592
18.2 Diffusion Modeling 595
18.3 Multi-scale Mass Transfer Modeling 598
18.3.1 Dimensionless Physical Parameter Groups 606
18.4 Summary 612
References 612
V ONLINE RESOURCES
Web Chapter 1: Waste and Emission Minimization
Web Chapter 2: Energy Storage and Control Systems
Web Chapter 3: Water Reuse, Footprint and Optimization Analysis
Case Study 1: Biomass CHP Plant Design Problem - LCA and Cost Analysis
Case Study 2: Comparison between Epoxy Resin Productions from Algal or Soya
Oil - An LCA Based Problem Solving Approach
Case Study 3: Waste Water Sludge Based CHP and Agricultural Application
System - An LCA Based Problem Solving Approach
Case Study 4: LCA Approach for Solar Organic Photovoltaic Cells
Manufacturing
Index 613