Jhuma Sadhukhan Centre for Environmental Strategy, University of Surrey, UKKok Siew Ng Centre for Process Integration, The University of Manchester, UKElias Martinez H. Centre for Environmental Strategy, University of Surrey, UK

“In conclusion, this book introduces the reader to the rapidly-developing industry of  biorefineries, with a multi-disciplinary approach. It is a good resource for undergraduate and post-graduate students who want to learn about biorefineries; it can also be valuable for researchers who are looking to practically apply these analytical tools in their work.”  (Green Process Synth, 4 February 2015)

• Preface xiii Acknowledgments xviiAbout the Authors xxiCompanionWebsite xxiiiNomenclature xxvI INTRODUCTION 11 Introduction 31.1 Fundamentals of the Biorefinery Concept 31.1.1 Biorefinery Principles 31.1.2 Biorefinery Types and Development 41.2 Biorefinery Features and Nomenclature 51.3 Biorefinery Feedstock: Biomass 71.3.1 Chemical Nature of Biorefinery Feedstocks 81.3.2 Feedstock Characterization 101.4 Processes and Platforms 121.5 Biorefinery Products 151.6 Optimization of Preprocessing and Fractionation for Bio Based Manufacturing 181.6.1 Background of Lignin 261.7 Electrochemistry Application in Biorefineries 311.8 Introduction to Energy and Water Systems 341.9 Evaluating Biorefinery Performances 361.9.1 Performance Indicators 361.9.2 Life Cycle Analysis 381.10 Chapters 381.11 Summary 38References 39II TOOLS 432 Economic Analysis 452.1 Introduction 452.2 General Economic Concepts and Terminology 462.2.1 Capital Cost and Battery Limits 462.2.2 Cost Index 462.2.3 Economies of Scale 472.2.4 Operating Cost 482.2.5 Cash Flows 492.2.6 Time Value of Money 492.2.7 Discounted Cash Flow Analysis and Net Present Value 502.2.8 Profitability Analysis 522.2.9 Learning Effect 532.3 Methodology 542.3.1 Capital Cost Estimation 542.3.2 Profitability Analysis 552.4 Cost Estimation and Correlation 552.4.1 Capital Cost 552.4.2 Operating Cost 582.5 Summary 592.6 Exercises 60References 613 Heat Integration and Utility System Design 633.1 Introduction 633.2 Process Integration 643.3 Analysis of Heat Exchanger Network Using Pinch Technology 653.3.1 Data Extraction 663.3.2 Construction of Temperature–Enthalpy Profiles 693.3.3 Application of the Graphical Approach for Energy Recovery 763.4 Utility System 833.4.1 Components in Utility System 833.5 Conceptual Design of Heat Recovery System for Cogeneration 883.5.1 Conventional Approach 883.5.2 Heuristic Based Approach 883.6 Summary 91References 914 Life Cycle Assessment 934.1 Life Cycle Thinking 934.2 Policy Context 964.3 Life Cycle Assessment (LCA) 964.4 LCA: Goal and Scope Definition 1004.5 LCA: Inventory Analysis 1044.6 LCA: Impact Assessment 1114.6.1 Global Warming Potential 1144.6.2 Land Use 1154.6.3 Resource Use 1194.6.4 Ozone Layer Depletion 1214.6.5 Acidification Potential 1234.6.6 Photochemical Oxidant Creation Potential 1264.6.7 Aquatic Ecotoxicity 1274.6.8 Eutrophication Potential 1274.6.9 Biodiversity 1284.7 LCA: Interpretation 1284.7.1 Stand-Alone LCA 1284.7.2 Accounting LCA 1294.7.3 Change Oriented LCA 1294.7.4 Allocation Method 1294.8 LCIA Methods 1304.9 Future R&D Needs 145References 1455 Data Uncertainty and Multicriteria Analyses 1475.1 Data Uncertainty Analysis 1475.1.1 Dominance Analysis 1485.1.2 Contribution Analysis 1495.1.3 Scenario Analysis 1515.1.4 Sensitivity Analysis 1535.1.5 Monte Carlo Simulation 1545.2 Multicriteria Analysis 1595.2.1 Economic Value and Environmental Impact Analysis of Biorefinery Systems 1605.2.2 Socioeconomic Analysis 1635.3 Summary 165References 1656 Value Analysis 1676.1 Value on Processing (VOP) and Cost of Production (COP) of Process Network Streams 1686.2 Value Analysis Heuristics 1726.2.1 Discounted Cash Flow Analysis 1736.3 Stream Economic Profile 1756.4 Concept of Boundary and Evaluation of Economic Margin of a Process Network 1756.5 Stream Profitability Analysis 1766.5.1 Value Analysis to Determine Necessary and Sufficient Condition for Streams to be Profitable or Nonprofitable 1816.6 Summary 187References 1877 Combined Economic Value and Environmental Impact (EVEI) Analysis 1897.1 Introduction 1897.2 Equivalency Between Economic and Environmental Impact Concepts 1907.3 Evaluation of Streams 1967.4 Environmental Impact Profile 2007.5 Product Economic Value and Environmental Impact (EVEI) Profile 2017.6 Summary 204References 2058 Optimization 2078.1 Introduction 2078.2 Linear Optimization 2088.2.1 Step 1: Rewriting in Standard LP Format 2108.2.2 Step 2: Initializing the Simplex Method 2118.2.3 Step 3: Obtaining an Initial Basic Solution 2128.2.4 Step 4: Determining Simplex Directions 2128.2.5 Step 5: Determining the Maximum Step Size by the Minimum Ratio Rule 2138.2.6 Step 6: Updating the Basic Variables 2148.3 Nonlinear Optimization 2188.3.1 Gradient Based Methods 2198.3.2 Generalized Reduced Gradient (GRG) Algorithm 2268.4 Mixed Integer Linear or Nonlinear Optimization 2398.4.1 Branch and Bound Method 2408.5 Stochastic Method 2438.5.1 Genetic Algorithm (GA) 2448.5.2 Non-dominated Sorting Genetic Algorithm (NSGA) Optimization 2468.5.3 GA in MATLAB 2488.6 Summary 248References 248III PROCESS SYNTHESIS AND DESIGN 2519 Generic Reactors: Thermochemical Processing of Biomass 2539.1 Introduction 2539.2 General Features of Thermochemical Conversion Processes 2549.3 Combustion 2579.4 Gasification 2589.4.1 The Process 2589.4.2 Types of Gasifier 2609.4.3 Design Considerations 2609.5 Pyrolysis 2629.5.1 What is Bio-Oil? 2629.5.2 How Is Bio-Oil Obtained from Biomass? 2649.5.3 How Fast Pyrolysis Works 2659.6 Summary 270Exercises 270References 27010 Reaction Thermodynamics 27110.1 Introduction 27110.2 Fundamentals of Design Calculation 27210.2.1 Heat of Combustion 27210.2.2 Higher and Lower Heating Values 27610.2.3 Adiabatic Flame Temperature 27810.2.4 Theoretical Air-to-Fuel Ratio 27910.2.5 Cold Gas Efficiency 28010.2.6 Hot Gas Efficiency 28110.2.7 Equivalence Ratio 28110.2.8 Carbon Conversion 28210.2.9 Heat of Reaction 28210.3 Process Design: Synthesis and Modeling 28210.3.1 Combustion Model 28210.3.2 Gasification Model 28310.3.3 Pyrolysis Model 28910.4 Summary 291Exercises 291References 29211 Reaction and Separation Process Synthesis: Chemical Production from Biomass 29511.1 Chemicals from Biomass: An Overview 29611.2 Bioreactor and Kinetics 29711.2.1 An Example of Lactic Acid Production 29911.2.2 An Example of Succinic Acid Production 30411.2.3 Heat Transfer Strategies for Reactors 30811.2.4 An Example of Ethylene Production 30911.2.5 An Example of Catalytic Fast Pyrolysis 31111.3 Controlled Acid Hydrolysis Reactions 31811.4 Advanced Separation and Reactive Separation 32711.4.1 Membrane Based Separations 32711.4.2 Membrane Filtration 33011.4.3 Electrodialysis 33311.4.4 Ion Exchange 33411.4.5 Integrated Processes 33811.4.6 Reactive Extraction 34111.4.7 Reactive Distillation 35211.4.8 Crystallization 35411.4.9 Precipitation 36011.5 Guidelines for Integrated Biorefinery Design 36011.5.1 An Example of Levulinic Acid Production: The Biofine Process 36511.6 Summary 368References 37012 Polymer Processes 37312.1 Polymer Concepts 37412.1.1 Polymer Classification 37512.1.2 Polymer Properties 37612.1.3 From Petrochemical Based Polymers to Biopolymers 37912.2 Modified Natural Biopolymers 38512.2.1 Starch Polymers 38512.2.2 Cellulose Polymers 38912.2.3 Natural Fiber and Lignin Composites 38912.3 Modeling of Polymerization Reaction Kinetics 39112.3.1 Chain-Growth or Addition Polymerization 39212.3.2 Step-Growth Polymerization 39612.3.3 Copolymerization 39812.4 Reactor Design for Biomass Based Monomers and Biopolymers 40012.4.1 Plug Flow Reactor (PFR) Design for Reaction in Gaseous Phase 40012.4.2 Bioreactor Design for Biopolymer Production – An Example of Polyhydroxyalkanoates 40212.4.3 Catalytic Reactor Design 40312.4.4 Energy Transfer Models of Reactors 41212.5 Synthesis of Unit Operations Combining Reaction and Separation Functionalities 41612.5.1 Reactive Distillation Column 41612.5.2 An Example of a Novel Reactor Arrangement 41812.6 Integrated Biopolymer Production in Biorefineries 42112.6.1 Polyesters 42112.6.2 Polyurethanes 42212.6.3 Polyamides 42212.6.4 Polycarbonates 42412.7 Summary 424References 42413 Separation Processes: Carbon Capture 42513.1 Absorption 42613.2 Absorption Process Flowsheet Synthesis 42913.3 The RectisolTM Technology 43113.3.1 Design and Operating Regions of RectisolTM Process 43313.3.2 Energy Consumption of a RectisolTM Process 43513.4 The SelexolTM Technology 44613.4.1 SelexolTM Process Parametric Analysis 44813.5 Adsorption Process 45713.5.1 Kinetic Modeling of SMR Reactions 45813.5.2 Adsorption Modeling of Carbon Dioxide 46013.5.3 Sorption Enhanced Reaction (SER) Process Dynamic Modeling Framework 46013.6 Chemical Looping Combustion 46313.7 Low Temperature Separation 47113.8 Summary 472References 473IV BIOREFINERY SYSTEMS 47514 Bio-Oil Refining I: Fischer–Tropsch Liquid and Methanol Synthesis 47714.1 Introduction 47714.2 Bio-Oil Upgrading 47814.2.1 Physical Upgrading 47814.2.2 Chemical Upgrading 47814.2.3 Biological Upgrading 48014.3 Distributed and Centralized Bio-Oil Processing Concept 48114.3.1 The Concept 48114.3.2 The Economics of Local Distribution of Bio-Oil 48214.3.3 The Economics of Importing Bio-Oil from Other Countries 48314.4 Integrated Thermochemical Processing of Bio-Oil into Fuels 48314.4.1 Synthetic Fuel Production 48414.4.2 Methanol Production 48514.5 Modeling, Integration and Analysis of Thermochemical Processes of Bio-Oil 48614.5.1 Flowsheet Synthesis and Modeling 48614.5.2 Sensitivity Analysis 48814.6 Summary 494References 49415 Bio-Oil Refining II: Novel Membrane Reactors 49715.1 Bio-Oil Co-Processing in Crude Oil Refinery 49715.2 Mixed Ionic Electronic Conducting (MIEC) Membrane for Hydrogen Production and Bio-Oil Hydrotreating and Hydrocracking 49915.3 Bio-Oil Hydrotreating and Hydrocracking Reaction Mechanisms and a MIEC Membrane Reactor Based Bio-Oil Upgrader Process Flowsheet 50215.4 A Coursework Problem 51015.5 Summary 513References 51416 Fuel Cells and Other Renewables 51516.1 Biomass Integrated Gasification Fuel Cell (BGFC) System Modeling for Design, Integration and Analysis 51716.2 Simulation of Integrated BGFC Flowsheets 52016.3 Heat Integration of BGFC Flowsheets 52816.4 Analysis of Processing Chains in BGFC Flowsheets 52916.5 SOFC Gibbs Free Energy Minimization Modeling 53216.6 Design of SOFC Based Micro-CHP Systems 53616.7 Fuel Cell and SOFC Design Parameterization Suitable for Spreadsheet Implementation 53716.7.1 Mass Balance 53916.7.2 Electrochemical Descriptions 54016.7.3 An air Blower Power Consumption 54216.7.4 Combustor Modeling 54316.7.5 Energy Balance 54316.8 Summary 546References 54617 Algae Biorefineries 54717.1 Algae Cultivation 54817.1.1 Open Pond Cultivation 54817.1.2 Photobioreactors (PBRs) 55617.2 Algae Harvesting and Oil Extraction 56217.2.1 Harvesting 56217.2.2 Extraction 57017.3 Algae Biodiesel Production 57017.3.1 Biodiesel Process 57017.3.2 Heterogeneous Catalysts for Transesterification 57217.4 Algae Biorefinery Integration 57217.5 Life Cycle Assessment of Algae Biorefineries 57517.6 Summary 579References 57918 Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling: Example of Biodiesel 58118.1 Intrinsic Kinetic Modeling 58218.1.1 Elementary Reaction Mechanism and Intrinsic Kinetic Modeling of the Biodiesel Production System 58218.1.2 Solution Strategy for the Rate Equations Resulting from the Elementary Reaction Mechanism 59018.1.3 Correlation between Concentration and Activity of Species Using the UNIQUAC Contribution Method 59118.1.4 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 59218.1.5 Intrinsic Kinetic Modeling Framework 59218.2 Diffusion Modeling 59518.3 Multi-scale Mass Transfer Modeling 59818.3.1 Dimensionless Physical Parameter Groups 60618.4 Summary 612References 612V ONLINE RESOURCESWeb Chapter 1: Waste and Emission MinimizationWeb Chapter 2: Energy Storage and Control SystemsWeb Chapter 3: Water Reuse, Footprint and Optimization AnalysisCase Study 1: Biomass CHP Plant Design Problem – LCA and Cost AnalysisCase Study 2: Comparison between Epoxy Resin Productions from Algal or Soya Oil – An LCA Based Problem Solving ApproachCase Study 3: Waste Water Sludge Based CHP and Agricultural Application System – An LCA Based Problem Solving ApproachCase Study 4: LCA Approach for Solar Organic Photovoltaic Cells ManufacturingIndex 613

Jhuma Sadhukhan Centre for Environmental Strategy, University of Surrey, UKKok Siew Ng Centre for Process Integration, The University of Manchester, UKElias Martinez H. Centre for Environmental Strategy, University of Surrey, UK

“In conclusion, this book introduces the reader to the rapidly-developing industry of  biorefineries, with a multi-disciplinary approach. It is a good resource for undergraduate and post-graduate students who want to learn about biorefineries; it can also be valuable for researchers who are looking to practically apply these analytical tools in their work.”  (Green Process Synth, 4 February 2015)

• Preface xiii Acknowledgments xviiAbout the Authors xxiCompanionWebsite xxiiiNomenclature xxvI INTRODUCTION 11 Introduction 31.1 Fundamentals of the Biorefinery Concept 31.1.1 Biorefinery Principles 31.1.2 Biorefinery Types and Development 41.2 Biorefinery Features and Nomenclature 51.3 Biorefinery Feedstock: Biomass 71.3.1 Chemical Nature of Biorefinery Feedstocks 81.3.2 Feedstock Characterization 101.4 Processes and Platforms 121.5 Biorefinery Products 151.6 Optimization of Preprocessing and Fractionation for Bio Based Manufacturing 181.6.1 Background of Lignin 261.7 Electrochemistry Application in Biorefineries 311.8 Introduction to Energy and Water Systems 341.9 Evaluating Biorefinery Performances 361.9.1 Performance Indicators 361.9.2 Life Cycle Analysis 381.10 Chapters 381.11 Summary 38References 39II TOOLS 432 Economic Analysis 452.1 Introduction 452.2 General Economic Concepts and Terminology 462.2.1 Capital Cost and Battery Limits 462.2.2 Cost Index 462.2.3 Economies of Scale 472.2.4 Operating Cost 482.2.5 Cash Flows 492.2.6 Time Value of Money 492.2.7 Discounted Cash Flow Analysis and Net Present Value 502.2.8 Profitability Analysis 522.2.9 Learning Effect 532.3 Methodology 542.3.1 Capital Cost Estimation 542.3.2 Profitability Analysis 552.4 Cost Estimation and Correlation 552.4.1 Capital Cost 552.4.2 Operating Cost 582.5 Summary 592.6 Exercises 60References 613 Heat Integration and Utility System Design 633.1 Introduction 633.2 Process Integration 643.3 Analysis of Heat Exchanger Network Using Pinch Technology 653.3.1 Data Extraction 663.3.2 Construction of Temperature–Enthalpy Profiles 693.3.3 Application of the Graphical Approach for Energy Recovery 763.4 Utility System 833.4.1 Components in Utility System 833.5 Conceptual Design of Heat Recovery System for Cogeneration 883.5.1 Conventional Approach 883.5.2 Heuristic Based Approach 883.6 Summary 91References 914 Life Cycle Assessment 934.1 Life Cycle Thinking 934.2 Policy Context 964.3 Life Cycle Assessment (LCA) 964.4 LCA: Goal and Scope Definition 1004.5 LCA: Inventory Analysis 1044.6 LCA: Impact Assessment 1114.6.1 Global Warming Potential 1144.6.2 Land Use 1154.6.3 Resource Use 1194.6.4 Ozone Layer Depletion 1214.6.5 Acidification Potential 1234.6.6 Photochemical Oxidant Creation Potential 1264.6.7 Aquatic Ecotoxicity 1274.6.8 Eutrophication Potential 1274.6.9 Biodiversity 1284.7 LCA: Interpretation 1284.7.1 Stand-Alone LCA 1284.7.2 Accounting LCA 1294.7.3 Change Oriented LCA 1294.7.4 Allocation Method 1294.8 LCIA Methods 1304.9 Future R&D Needs 145References 1455 Data Uncertainty and Multicriteria Analyses 1475.1 Data Uncertainty Analysis 1475.1.1 Dominance Analysis 1485.1.2 Contribution Analysis 1495.1.3 Scenario Analysis 1515.1.4 Sensitivity Analysis 1535.1.5 Monte Carlo Simulation 1545.2 Multicriteria Analysis 1595.2.1 Economic Value and Environmental Impact Analysis of Biorefinery Systems 1605.2.2 Socioeconomic Analysis 1635.3 Summary 165References 1656 Value Analysis 1676.1 Value on Processing (VOP) and Cost of Production (COP) of Process Network Streams 1686.2 Value Analysis Heuristics 1726.2.1 Discounted Cash Flow Analysis 1736.3 Stream Economic Profile 1756.4 Concept of Boundary and Evaluation of Economic Margin of a Process Network 1756.5 Stream Profitability Analysis 1766.5.1 Value Analysis to Determine Necessary and Sufficient Condition for Streams to be Profitable or Nonprofitable 1816.6 Summary 187References 1877 Combined Economic Value and Environmental Impact (EVEI) Analysis 1897.1 Introduction 1897.2 Equivalency Between Economic and Environmental Impact Concepts 1907.3 Evaluation of Streams 1967.4 Environmental Impact Profile 2007.5 Product Economic Value and Environmental Impact (EVEI) Profile 2017.6 Summary 204References 2058 Optimization 2078.1 Introduction 2078.2 Linear Optimization 2088.2.1 Step 1: Rewriting in Standard LP Format 2108.2.2 Step 2: Initializing the Simplex Method 2118.2.3 Step 3: Obtaining an Initial Basic Solution 2128.2.4 Step 4: Determining Simplex Directions 2128.2.5 Step 5: Determining the Maximum Step Size by the Minimum Ratio Rule 2138.2.6 Step 6: Updating the Basic Variables 2148.3 Nonlinear Optimization 2188.3.1 Gradient Based Methods 2198.3.2 Generalized Reduced Gradient (GRG) Algorithm 2268.4 Mixed Integer Linear or Nonlinear Optimization 2398.4.1 Branch and Bound Method 2408.5 Stochastic Method 2438.5.1 Genetic Algorithm (GA) 2448.5.2 Non-dominated Sorting Genetic Algorithm (NSGA) Optimization 2468.5.3 GA in MATLAB 2488.6 Summary 248References 248III PROCESS SYNTHESIS AND DESIGN 2519 Generic Reactors: Thermochemical Processing of Biomass 2539.1 Introduction 2539.2 General Features of Thermochemical Conversion Processes 2549.3 Combustion 2579.4 Gasification 2589.4.1 The Process 2589.4.2 Types of Gasifier 2609.4.3 Design Considerations 2609.5 Pyrolysis 2629.5.1 What is Bio-Oil? 2629.5.2 How Is Bio-Oil Obtained from Biomass? 2649.5.3 How Fast Pyrolysis Works 2659.6 Summary 270Exercises 270References 27010 Reaction Thermodynamics 27110.1 Introduction 27110.2 Fundamentals of Design Calculation 27210.2.1 Heat of Combustion 27210.2.2 Higher and Lower Heating Values 27610.2.3 Adiabatic Flame Temperature 27810.2.4 Theoretical Air-to-Fuel Ratio 27910.2.5 Cold Gas Efficiency 28010.2.6 Hot Gas Efficiency 28110.2.7 Equivalence Ratio 28110.2.8 Carbon Conversion 28210.2.9 Heat of Reaction 28210.3 Process Design: Synthesis and Modeling 28210.3.1 Combustion Model 28210.3.2 Gasification Model 28310.3.3 Pyrolysis Model 28910.4 Summary 291Exercises 291References 29211 Reaction and Separation Process Synthesis: Chemical Production from Biomass 29511.1 Chemicals from Biomass: An Overview 29611.2 Bioreactor and Kinetics 29711.2.1 An Example of Lactic Acid Production 29911.2.2 An Example of Succinic Acid Production 30411.2.3 Heat Transfer Strategies for Reactors 30811.2.4 An Example of Ethylene Production 30911.2.5 An Example of Catalytic Fast Pyrolysis 31111.3 Controlled Acid Hydrolysis Reactions 31811.4 Advanced Separation and Reactive Separation 32711.4.1 Membrane Based Separations 32711.4.2 Membrane Filtration 33011.4.3 Electrodialysis 33311.4.4 Ion Exchange 33411.4.5 Integrated Processes 33811.4.6 Reactive Extraction 34111.4.7 Reactive Distillation 35211.4.8 Crystallization 35411.4.9 Precipitation 36011.5 Guidelines for Integrated Biorefinery Design 36011.5.1 An Example of Levulinic Acid Production: The Biofine Process 36511.6 Summary 368References 37012 Polymer Processes 37312.1 Polymer Concepts 37412.1.1 Polymer Classification 37512.1.2 Polymer Properties 37612.1.3 From Petrochemical Based Polymers to Biopolymers 37912.2 Modified Natural Biopolymers 38512.2.1 Starch Polymers 38512.2.2 Cellulose Polymers 38912.2.3 Natural Fiber and Lignin Composites 38912.3 Modeling of Polymerization Reaction Kinetics 39112.3.1 Chain-Growth or Addition Polymerization 39212.3.2 Step-Growth Polymerization 39612.3.3 Copolymerization 39812.4 Reactor Design for Biomass Based Monomers and Biopolymers 40012.4.1 Plug Flow Reactor (PFR) Design for Reaction in Gaseous Phase 40012.4.2 Bioreactor Design for Biopolymer Production – An Example of Polyhydroxyalkanoates 40212.4.3 Catalytic Reactor Design 40312.4.4 Energy Transfer Models of Reactors 41212.5 Synthesis of Unit Operations Combining Reaction and Separation Functionalities 41612.5.1 Reactive Distillation Column 41612.5.2 An Example of a Novel Reactor Arrangement 41812.6 Integrated Biopolymer Production in Biorefineries 42112.6.1 Polyesters 42112.6.2 Polyurethanes 42212.6.3 Polyamides 42212.6.4 Polycarbonates 42412.7 Summary 424References 42413 Separation Processes: Carbon Capture 42513.1 Absorption 42613.2 Absorption Process Flowsheet Synthesis 42913.3 The RectisolTM Technology 43113.3.1 Design and Operating Regions of RectisolTM Process 43313.3.2 Energy Consumption of a RectisolTM Process 43513.4 The SelexolTM Technology 44613.4.1 SelexolTM Process Parametric Analysis 44813.5 Adsorption Process 45713.5.1 Kinetic Modeling of SMR Reactions 45813.5.2 Adsorption Modeling of Carbon Dioxide 46013.5.3 Sorption Enhanced Reaction (SER) Process Dynamic Modeling Framework 46013.6 Chemical Looping Combustion 46313.7 Low Temperature Separation 47113.8 Summary 472References 473IV BIOREFINERY SYSTEMS 47514 Bio-Oil Refining I: Fischer–Tropsch Liquid and Methanol Synthesis 47714.1 Introduction 47714.2 Bio-Oil Upgrading 47814.2.1 Physical Upgrading 47814.2.2 Chemical Upgrading 47814.2.3 Biological Upgrading 48014.3 Distributed and Centralized Bio-Oil Processing Concept 48114.3.1 The Concept 48114.3.2 The Economics of Local Distribution of Bio-Oil 48214.3.3 The Economics of Importing Bio-Oil from Other Countries 48314.4 Integrated Thermochemical Processing of Bio-Oil into Fuels 48314.4.1 Synthetic Fuel Production 48414.4.2 Methanol Production 48514.5 Modeling, Integration and Analysis of Thermochemical Processes of Bio-Oil 48614.5.1 Flowsheet Synthesis and Modeling 48614.5.2 Sensitivity Analysis 48814.6 Summary 494References 49415 Bio-Oil Refining II: Novel Membrane Reactors 49715.1 Bio-Oil Co-Processing in Crude Oil Refinery 49715.2 Mixed Ionic Electronic Conducting (MIEC) Membrane for Hydrogen Production and Bio-Oil Hydrotreating and Hydrocracking 49915.3 Bio-Oil Hydrotreating and Hydrocracking Reaction Mechanisms and a MIEC Membrane Reactor Based Bio-Oil Upgrader Process Flowsheet 50215.4 A Coursework Problem 51015.5 Summary 513References 51416 Fuel Cells and Other Renewables 51516.1 Biomass Integrated Gasification Fuel Cell (BGFC) System Modeling for Design, Integration and Analysis 51716.2 Simulation of Integrated BGFC Flowsheets 52016.3 Heat Integration of BGFC Flowsheets 52816.4 Analysis of Processing Chains in BGFC Flowsheets 52916.5 SOFC Gibbs Free Energy Minimization Modeling 53216.6 Design of SOFC Based Micro-CHP Systems 53616.7 Fuel Cell and SOFC Design Parameterization Suitable for Spreadsheet Implementation 53716.7.1 Mass Balance 53916.7.2 Electrochemical Descriptions 54016.7.3 An air Blower Power Consumption 54216.7.4 Combustor Modeling 54316.7.5 Energy Balance 54316.8 Summary 546References 54617 Algae Biorefineries 54717.1 Algae Cultivation 54817.1.1 Open Pond Cultivation 54817.1.2 Photobioreactors (PBRs) 55617.2 Algae Harvesting and Oil Extraction 56217.2.1 Harvesting 56217.2.2 Extraction 57017.3 Algae Biodiesel Production 57017.3.1 Biodiesel Process 57017.3.2 Heterogeneous Catalysts for Transesterification 57217.4 Algae Biorefinery Integration 57217.5 Life Cycle Assessment of Algae Biorefineries 57517.6 Summary 579References 57918 Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling: Example of Biodiesel 58118.1 Intrinsic Kinetic Modeling 58218.1.1 Elementary Reaction Mechanism and Intrinsic Kinetic Modeling of the Biodiesel Production System 58218.1.2 Solution Strategy for the Rate Equations Resulting from the Elementary Reaction Mechanism 59018.1.3 Correlation between Concentration and Activity of Species Using the UNIQUAC Contribution Method 59118.1.4 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 59218.1.5 Intrinsic Kinetic Modeling Framework 59218.2 Diffusion Modeling 59518.3 Multi-scale Mass Transfer Modeling 59818.3.1 Dimensionless Physical Parameter Groups 60618.4 Summary 612References 612V ONLINE RESOURCESWeb Chapter 1: Waste and Emission MinimizationWeb Chapter 2: Energy Storage and Control SystemsWeb Chapter 3: Water Reuse, Footprint and Optimization AnalysisCase Study 1: Biomass CHP Plant Design Problem – LCA and Cost AnalysisCase Study 2: Comparison between Epoxy Resin Productions from Algal or Soya Oil – An LCA Based Problem Solving ApproachCase Study 3: Waste Water Sludge Based CHP and Agricultural Application System – An LCA Based Problem Solving ApproachCase Study 4: LCA Approach for Solar Organic Photovoltaic Cells ManufacturingIndex 613

Jhuma Sadhukhan Centre for Environmental Strategy, University of Surrey, UKKok Siew Ng Centre for Process Integration, The University of Manchester, UKElias Martinez H. Centre for Environmental Strategy, University of Surrey, UK

“In conclusion, this book introduces the reader to the rapidly-developing industry of  biorefineries, with a multi-disciplinary approach. It is a good resource for undergraduate and post-graduate students who want to learn about biorefineries; it can also be valuable for researchers who are looking to practically apply these analytical tools in their work.”  (Green Process Synth, 4 February 2015)

• Preface xiii Acknowledgments xviiAbout the Authors xxiCompanionWebsite xxiiiNomenclature xxvI INTRODUCTION 11 Introduction 31.1 Fundamentals of the Biorefinery Concept 31.1.1 Biorefinery Principles 31.1.2 Biorefinery Types and Development 41.2 Biorefinery Features and Nomenclature 51.3 Biorefinery Feedstock: Biomass 71.3.1 Chemical Nature of Biorefinery Feedstocks 81.3.2 Feedstock Characterization 101.4 Processes and Platforms 121.5 Biorefinery Products 151.6 Optimization of Preprocessing and Fractionation for Bio Based Manufacturing 181.6.1 Background of Lignin 261.7 Electrochemistry Application in Biorefineries 311.8 Introduction to Energy and Water Systems 341.9 Evaluating Biorefinery Performances 361.9.1 Performance Indicators 361.9.2 Life Cycle Analysis 381.10 Chapters 381.11 Summary 38References 39II TOOLS 432 Economic Analysis 452.1 Introduction 452.2 General Economic Concepts and Terminology 462.2.1 Capital Cost and Battery Limits 462.2.2 Cost Index 462.2.3 Economies of Scale 472.2.4 Operating Cost 482.2.5 Cash Flows 492.2.6 Time Value of Money 492.2.7 Discounted Cash Flow Analysis and Net Present Value 502.2.8 Profitability Analysis 522.2.9 Learning Effect 532.3 Methodology 542.3.1 Capital Cost Estimation 542.3.2 Profitability Analysis 552.4 Cost Estimation and Correlation 552.4.1 Capital Cost 552.4.2 Operating Cost 582.5 Summary 592.6 Exercises 60References 613 Heat Integration and Utility System Design 633.1 Introduction 633.2 Process Integration 643.3 Analysis of Heat Exchanger Network Using Pinch Technology 653.3.1 Data Extraction 663.3.2 Construction of Temperature–Enthalpy Profiles 693.3.3 Application of the Graphical Approach for Energy Recovery 763.4 Utility System 833.4.1 Components in Utility System 833.5 Conceptual Design of Heat Recovery System for Cogeneration 883.5.1 Conventional Approach 883.5.2 Heuristic Based Approach 883.6 Summary 91References 914 Life Cycle Assessment 934.1 Life Cycle Thinking 934.2 Policy Context 964.3 Life Cycle Assessment (LCA) 964.4 LCA: Goal and Scope Definition 1004.5 LCA: Inventory Analysis 1044.6 LCA: Impact Assessment 1114.6.1 Global Warming Potential 1144.6.2 Land Use 1154.6.3 Resource Use 1194.6.4 Ozone Layer Depletion 1214.6.5 Acidification Potential 1234.6.6 Photochemical Oxidant Creation Potential 1264.6.7 Aquatic Ecotoxicity 1274.6.8 Eutrophication Potential 1274.6.9 Biodiversity 1284.7 LCA: Interpretation 1284.7.1 Stand-Alone LCA 1284.7.2 Accounting LCA 1294.7.3 Change Oriented LCA 1294.7.4 Allocation Method 1294.8 LCIA Methods 1304.9 Future R&D Needs 145References 1455 Data Uncertainty and Multicriteria Analyses 1475.1 Data Uncertainty Analysis 1475.1.1 Dominance Analysis 1485.1.2 Contribution Analysis 1495.1.3 Scenario Analysis 1515.1.4 Sensitivity Analysis 1535.1.5 Monte Carlo Simulation 1545.2 Multicriteria Analysis 1595.2.1 Economic Value and Environmental Impact Analysis of Biorefinery Systems 1605.2.2 Socioeconomic Analysis 1635.3 Summary 165References 1656 Value Analysis 1676.1 Value on Processing (VOP) and Cost of Production (COP) of Process Network Streams 1686.2 Value Analysis Heuristics 1726.2.1 Discounted Cash Flow Analysis 1736.3 Stream Economic Profile 1756.4 Concept of Boundary and Evaluation of Economic Margin of a Process Network 1756.5 Stream Profitability Analysis 1766.5.1 Value Analysis to Determine Necessary and Sufficient Condition for Streams to be Profitable or Nonprofitable 1816.6 Summary 187References 1877 Combined Economic Value and Environmental Impact (EVEI) Analysis 1897.1 Introduction 1897.2 Equivalency Between Economic and Environmental Impact Concepts 1907.3 Evaluation of Streams 1967.4 Environmental Impact Profile 2007.5 Product Economic Value and Environmental Impact (EVEI) Profile 2017.6 Summary 204References 2058 Optimization 2078.1 Introduction 2078.2 Linear Optimization 2088.2.1 Step 1: Rewriting in Standard LP Format 2108.2.2 Step 2: Initializing the Simplex Method 2118.2.3 Step 3: Obtaining an Initial Basic Solution 2128.2.4 Step 4: Determining Simplex Directions 2128.2.5 Step 5: Determining the Maximum Step Size by the Minimum Ratio Rule 2138.2.6 Step 6: Updating the Basic Variables 2148.3 Nonlinear Optimization 2188.3.1 Gradient Based Methods 2198.3.2 Generalized Reduced Gradient (GRG) Algorithm 2268.4 Mixed Integer Linear or Nonlinear Optimization 2398.4.1 Branch and Bound Method 2408.5 Stochastic Method 2438.5.1 Genetic Algorithm (GA) 2448.5.2 Non-dominated Sorting Genetic Algorithm (NSGA) Optimization 2468.5.3 GA in MATLAB 2488.6 Summary 248References 248III PROCESS SYNTHESIS AND DESIGN 2519 Generic Reactors: Thermochemical Processing of Biomass 2539.1 Introduction 2539.2 General Features of Thermochemical Conversion Processes 2549.3 Combustion 2579.4 Gasification 2589.4.1 The Process 2589.4.2 Types of Gasifier 2609.4.3 Design Considerations 2609.5 Pyrolysis 2629.5.1 What is Bio-Oil? 2629.5.2 How Is Bio-Oil Obtained from Biomass? 2649.5.3 How Fast Pyrolysis Works 2659.6 Summary 270Exercises 270References 27010 Reaction Thermodynamics 27110.1 Introduction 27110.2 Fundamentals of Design Calculation 27210.2.1 Heat of Combustion 27210.2.2 Higher and Lower Heating Values 27610.2.3 Adiabatic Flame Temperature 27810.2.4 Theoretical Air-to-Fuel Ratio 27910.2.5 Cold Gas Efficiency 28010.2.6 Hot Gas Efficiency 28110.2.7 Equivalence Ratio 28110.2.8 Carbon Conversion 28210.2.9 Heat of Reaction 28210.3 Process Design: Synthesis and Modeling 28210.3.1 Combustion Model 28210.3.2 Gasification Model 28310.3.3 Pyrolysis Model 28910.4 Summary 291Exercises 291References 29211 Reaction and Separation Process Synthesis: Chemical Production from Biomass 29511.1 Chemicals from Biomass: An Overview 29611.2 Bioreactor and Kinetics 29711.2.1 An Example of Lactic Acid Production 29911.2.2 An Example of Succinic Acid Production 30411.2.3 Heat Transfer Strategies for Reactors 30811.2.4 An Example of Ethylene Production 30911.2.5 An Example of Catalytic Fast Pyrolysis 31111.3 Controlled Acid Hydrolysis Reactions 31811.4 Advanced Separation and Reactive Separation 32711.4.1 Membrane Based Separations 32711.4.2 Membrane Filtration 33011.4.3 Electrodialysis 33311.4.4 Ion Exchange 33411.4.5 Integrated Processes 33811.4.6 Reactive Extraction 34111.4.7 Reactive Distillation 35211.4.8 Crystallization 35411.4.9 Precipitation 36011.5 Guidelines for Integrated Biorefinery Design 36011.5.1 An Example of Levulinic Acid Production: The Biofine Process 36511.6 Summary 368References 37012 Polymer Processes 37312.1 Polymer Concepts 37412.1.1 Polymer Classification 37512.1.2 Polymer Properties 37612.1.3 From Petrochemical Based Polymers to Biopolymers 37912.2 Modified Natural Biopolymers 38512.2.1 Starch Polymers 38512.2.2 Cellulose Polymers 38912.2.3 Natural Fiber and Lignin Composites 38912.3 Modeling of Polymerization Reaction Kinetics 39112.3.1 Chain-Growth or Addition Polymerization 39212.3.2 Step-Growth Polymerization 39612.3.3 Copolymerization 39812.4 Reactor Design for Biomass Based Monomers and Biopolymers 40012.4.1 Plug Flow Reactor (PFR) Design for Reaction in Gaseous Phase 40012.4.2 Bioreactor Design for Biopolymer Production – An Example of Polyhydroxyalkanoates 40212.4.3 Catalytic Reactor Design 40312.4.4 Energy Transfer Models of Reactors 41212.5 Synthesis of Unit Operations Combining Reaction and Separation Functionalities 41612.5.1 Reactive Distillation Column 41612.5.2 An Example of a Novel Reactor Arrangement 41812.6 Integrated Biopolymer Production in Biorefineries 42112.6.1 Polyesters 42112.6.2 Polyurethanes 42212.6.3 Polyamides 42212.6.4 Polycarbonates 42412.7 Summary 424References 42413 Separation Processes: Carbon Capture 42513.1 Absorption 42613.2 Absorption Process Flowsheet Synthesis 42913.3 The RectisolTM Technology 43113.3.1 Design and Operating Regions of RectisolTM Process 43313.3.2 Energy Consumption of a RectisolTM Process 43513.4 The SelexolTM Technology 44613.4.1 SelexolTM Process Parametric Analysis 44813.5 Adsorption Process 45713.5.1 Kinetic Modeling of SMR Reactions 45813.5.2 Adsorption Modeling of Carbon Dioxide 46013.5.3 Sorption Enhanced Reaction (SER) Process Dynamic Modeling Framework 46013.6 Chemical Looping Combustion 46313.7 Low Temperature Separation 47113.8 Summary 472References 473IV BIOREFINERY SYSTEMS 47514 Bio-Oil Refining I: Fischer–Tropsch Liquid and Methanol Synthesis 47714.1 Introduction 47714.2 Bio-Oil Upgrading 47814.2.1 Physical Upgrading 47814.2.2 Chemical Upgrading 47814.2.3 Biological Upgrading 48014.3 Distributed and Centralized Bio-Oil Processing Concept 48114.3.1 The Concept 48114.3.2 The Economics of Local Distribution of Bio-Oil 48214.3.3 The Economics of Importing Bio-Oil from Other Countries 48314.4 Integrated Thermochemical Processing of Bio-Oil into Fuels 48314.4.1 Synthetic Fuel Production 48414.4.2 Methanol Production 48514.5 Modeling, Integration and Analysis of Thermochemical Processes of Bio-Oil 48614.5.1 Flowsheet Synthesis and Modeling 48614.5.2 Sensitivity Analysis 48814.6 Summary 494References 49415 Bio-Oil Refining II: Novel Membrane Reactors 49715.1 Bio-Oil Co-Processing in Crude Oil Refinery 49715.2 Mixed Ionic Electronic Conducting (MIEC) Membrane for Hydrogen Production and Bio-Oil Hydrotreating and Hydrocracking 49915.3 Bio-Oil Hydrotreating and Hydrocracking Reaction Mechanisms and a MIEC Membrane Reactor Based Bio-Oil Upgrader Process Flowsheet 50215.4 A Coursework Problem 51015.5 Summary 513References 51416 Fuel Cells and Other Renewables 51516.1 Biomass Integrated Gasification Fuel Cell (BGFC) System Modeling for Design, Integration and Analysis 51716.2 Simulation of Integrated BGFC Flowsheets 52016.3 Heat Integration of BGFC Flowsheets 52816.4 Analysis of Processing Chains in BGFC Flowsheets 52916.5 SOFC Gibbs Free Energy Minimization Modeling 53216.6 Design of SOFC Based Micro-CHP Systems 53616.7 Fuel Cell and SOFC Design Parameterization Suitable for Spreadsheet Implementation 53716.7.1 Mass Balance 53916.7.2 Electrochemical Descriptions 54016.7.3 An air Blower Power Consumption 54216.7.4 Combustor Modeling 54316.7.5 Energy Balance 54316.8 Summary 546References 54617 Algae Biorefineries 54717.1 Algae Cultivation 54817.1.1 Open Pond Cultivation 54817.1.2 Photobioreactors (PBRs) 55617.2 Algae Harvesting and Oil Extraction 56217.2.1 Harvesting 56217.2.2 Extraction 57017.3 Algae Biodiesel Production 57017.3.1 Biodiesel Process 57017.3.2 Heterogeneous Catalysts for Transesterification 57217.4 Algae Biorefinery Integration 57217.5 Life Cycle Assessment of Algae Biorefineries 57517.6 Summary 579References 57918 Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling: Example of Biodiesel 58118.1 Intrinsic Kinetic Modeling 58218.1.1 Elementary Reaction Mechanism and Intrinsic Kinetic Modeling of the Biodiesel Production System 58218.1.2 Solution Strategy for the Rate Equations Resulting from the Elementary Reaction Mechanism 59018.1.3 Correlation between Concentration and Activity of Species Using the UNIQUAC Contribution Method 59118.1.4 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 59218.1.5 Intrinsic Kinetic Modeling Framework 59218.2 Diffusion Modeling 59518.3 Multi-scale Mass Transfer Modeling 59818.3.1 Dimensionless Physical Parameter Groups 60618.4 Summary 612References 612V ONLINE RESOURCESWeb Chapter 1: Waste and Emission MinimizationWeb Chapter 2: Energy Storage and Control SystemsWeb Chapter 3: Water Reuse, Footprint and Optimization AnalysisCase Study 1: Biomass CHP Plant Design Problem – LCA and Cost AnalysisCase Study 2: Comparison between Epoxy Resin Productions from Algal or Soya Oil – An LCA Based Problem Solving ApproachCase Study 3: Waste Water Sludge Based CHP and Agricultural Application System – An LCA Based Problem Solving ApproachCase Study 4: LCA Approach for Solar Organic Photovoltaic Cells ManufacturingIndex 613