Biorefineries and Chemical Processes Design, Integration and Sustainability Analysis

As the range of feedstocks, process technologies and products expand, biorefineries will become increasingly complex manufacturing systems. Biorefineries 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.

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