GREEN CHEMISTRY AND ENGINEERING

GREEN CHEMISTRY AND ENGINEERING

GREEN CHEMISTRY AND ENGINEERING A Practical Design Approach CONCEPCIÓN JIMÉNEZ-GONZÁLEZ DAVID J. C. CONSTABLE

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CONTENTS PREFACE xi PART I GREEEN CHEMISTRY AND GREEN ENGINEERING IN THE MOVEMENT TOWARD SUSTAINABILITY 1 1 Green Chemistry and Engineering in the Context of Sustainability 3 1.1 Why Green Chemistry? 3 1.2 Green Chemistry, Green Engineering, and Sustainability 6 1.3 Until Death Do Us Part: A Marriage of Disciplines 13 Problems 15 References 15 2 Green Chemistry and Green Engineering Principles 17 2.1 Green Chemistry Principles 17 2.2 Twelve More Green Chemistry Principles 26 2.3 Twelve Principles of Green Engineering 28 2.4 The San Destin Declaration: Principles of Green Engineering 31 2.5 Simplifying the Principles 34 Problems 38 References 39 3 Starting with the Basics: Integrating Environment, Health, and Safety 41 3.1 Environmental Issues of Importance 42 3.2 Health Issues of Importance 54 v

vi CONTENTS 3.3 Safety Issues of Importance 62 3.4 Hazard and Risk 68 3.5 Integrated Perspective on Environment, Health, and Safety 70 Problems 70 References 73 4 How Do We Know It s Green? A Metrics Primer 77 4.1 General Considerations About Green Chemistry and Engineering Metrics 77 4.2 Chemistry Metrics 79 4.3 Process Metrics 89 4.4 Cost Implications and Green Chemistry Metrics 101 4.5 A Final Word on Green Metrics 101 Problems 102 References 103 PART II THE BEGINNING: DESIGNING GREENER, SAFER CHEMICAL SYNTHESES 107 5 Route and Chemistry Selection 109 5.1 The Challenge of Synthetic Chemistry 109 5.2 Making Molecules 110 5.3 Using Different Chemistries 119 5.4 Route Strategy 122 5.5 Protection Deprotection 124 5.6 Going from a Route to a Process 126 Problems 127 References 130 6 Material Selection: Solvents, Catalysts, and Reagents 133 6.1 Solvents and Solvent Selection Strategies 133 6.2 Catalysts and Catalyst Selection Strategies 154 6.3 Other Reagents 168 Problems 168 References 173 7 Reaction Conditions and Green Chemistry 175 7.1 Stoichiometry 176 7.2 Design of Experiments 178 7.3 Temperature 180 7.4 Solvent Use 182 7.5 Solvents and Energy Use 184 7.6 Reaction and Processing Time 187 7.7 Order and Rate of Reagent Addition 188 7.8 Mixing 189

CONTENTS vii Appendix 7.1: Common Practices in Batch Chemical Processing and Their Green Chemistry Impacts 191 Problems 196 References 200 8 Bioprocesses 203 8.1 How Biotechnology Has Been Used 203 8.2 Are Bioprocesses Green? 204 8.3 What Is Involved in Bioprocessing 205 8.4 Examples of Products Obtained from Bioprocessing 216 Problems 226 References 232 PART III FROM THE FLASK TO THE PLANT: DESIGNING GREENER, SAFER, MORE SUSTAINABLE MANUFACTURING PROCESSES 233 9 Mass and Energy Balances 235 9.1 Why We Need Mass Balances, Energy Balances, and Process Flow Diagrams 236 9.2 Types of Processes 237 9.3 Process Flow Diagams 238 9.4 Mass Balances 241 9.5 Energy Balances 250 9.6 Measuring Greenness of a Process Through Energy and Mass Balances 261 Problems 265 References 272 10 The Scale-up Effect 273 10.1 The Scale-up Problem 273 10.2 Factors Affecting Scale-up 276 10.3 Scale-up Tools 283 10.4 Numbering-up vs. Scaling-up 289 Problems 290 References 293 11 Reactors and Separations 295 11.1 Reactors and Separations in Green Engineering 296 11.2 Reactors 296 11.3 Separations and Other Unit Operations 307 11.4 Batch vs. Continuous Processes 321 11.5 Does Size Matter? 323 Problems 323 References 327

viii CONTENTS 12 Process Synthesis 331 12.1 Process Synthesis Background 331 12.2 Process Synthesis Approaches and Green Engineering 333 12.3 Evolutionary Techniques 334 12.4 Heuristics Methods 343 12.5 Hierarchical Decomposition 346 12.6 Superstructure and Multiobjective Optimization 349 12.7 Synthesis of Subsystems 354 Problems 355 References 359 13 Mass and Energy Integration 363 13.1 Process Integration: Synthesis, Analysis, and Optimization 363 13.2 Energy Integration 365 13.3 Mass Integration 373 Problems 381 References 388 14 Inherent Safety 391 14.1 Inherent Safety vs. Traditional Process Safety 391 14.2 Inherent Safety and Inherently Safer Design 394 14.3 Inherent Safety in Route Strategy and Process Design 398 14.4 Conclusions on Inherent Safety 406 Problems 406 References 411 15 Process Intensification 413 15.1 Process Intensification Background 413 15.2 Process Intensification Technologies 416 15.3 Process Intensification Techniques 435 15.4 Perspectives on Process Intensification 437 Problems 437 References 442 PART IV EXPANDING THE BOUNDARIES 447 16 Life Cycle Inventory and Assessment Concepts 449 16.1 Life Cycle Inventory and Assessment Background 450 16.2 LCI/A Methodology 452 16.3 Interpretation: Making Decisions with LCI/A 473 16.4 Streamlined Life Cycle Assessment 481 Problems 484 References 488

CONTENTS ix 17 Impacts of Materials and Procurement 493 17.1 Life Cycle Management 493 17.2 Where Chemical Trees and Supply Chains Come From 495 17.3 Green (Sustainable) Procurement 500 17.4 Transportation Impacts 511 Problems 515 References 517 18 Impacts of Energy Requirements 519 18.1 Where Energy Comes From 519 18.2 Environmental Life Cycle Emissions and Impacts of Energy Generation 525 18.3 From Emissions to Impacts 537 18.4 Energy Requirements for Waste Treatment 540 Problems 540 References 542 19 Impacts of Waste and Waste Treatment 545 19.1 Environmental Fate and Effects Data 546 19.2 Environmental Fate Information: Physical Properties 550 19.3 Environmental Fate Information: Transformation and Depletion Mechanisms 557 19.4 Environmental Effects Information 559 19.5 Environmental Risk Assessment 562 19.6 Environmental Life Cycle Impacts of Waste Treatment 565 Problems 574 References 576 20 Total Cost Assessment 579 20.1 Total Cost Assessment Background 579 20.2 Importance of Total Cost Assessment 580 20.3 Relationship Between Life Cycle Inventory/Assessment and Total Cost Assessment 582 20.4 Timing of a Total Cost Assessment 583 20.5 Total Cost Assessment Methodology 583 20.6 Total Cost Assessment in a Green Chemistry Context 589 Problems 594 References 597 PART V WHAT LIES AHEAD 599 21 Emerging Materials 601 21.1 Emerging Materials Development 601 21.2 Nanomaterials 602

x CONTENTS 21.3 Bioplastics and Biopolymers 605 21.4 About New Green Materials 609 Problems 609 References 611 22 Renewable Resources 613 22.1 Why We Need Renewable Resources 613 22.2 Renewable Materials 616 22.3 The Biorefinery 621 22.4 Renewable Energy 625 Problems 630 References 632 23 Evaluating Technologies 635 23.1 Why We Need to Evaluate Technologies and Processes Comprehensively 635 23.2 Comparing Technologies and Processes 636 23.3 One Way to Compare Technologies 637 23.4 Trade-Offs 644 23.5 Advantages and Limitations of Comparing Technologies 645 Problems 646 References 649 24 Industrial Ecology 651 24.1 Industrial Ecology Background 652 24.2 Principles and Concepts of Industrial Ecology and Design 655 24.3 Industrial Ecology and Design 657 24.4 Industrial Ecology in Practice 663 Problems 665 References 666 25 Tying It All Together: Is Sustainability Possible? 669 25.1 Can Green Chemistry and Green Engineering Enable Sustainability? 670 25.2 Sustainability: Culture and Policy 671 25.3 Influencing Sustainability 672 25.4 Moving to Action 674 Problems 674 References 675 INDEX 677

PREFACE In the last decade, interest in and understanding of green chemistry and green engineering have increased steadily beyond academia and into the business world. Industries within different sectors of the economy have made concerted efforts to embed these concepts in their operations. Given our experience with green chemistry and green engineering in the pharmaceutical industry, we were initially approached by the publishers to edit a book on green chemistry in the pharmaceutical industry. This was a worthy proposal, but we felt that we had a greater opportunity and worthier endeavor to produce a book that would attempt to fully integrate green chemistry and green engineering into the academic curricula and that at the same time could serve as a practical reference to chemists and engineers in the workplace. Green chemistry and green engineering are still relatively new areas that have not been completely ingrained in traditional chemistry and engineering curricula, but classes and even majors in these topics are becoming increasingly common. However, most classes in green chemistry are taught from an environmental chemistry perspective or a synthetic organic chemistry perspective, with neither approach addressing issues of manufacturing or manufacturability of products. Green engineering classes, on the other hand, tend to emphasize issues related to manufacturing, but do not treat reaction and process chemistry sufficiently, so these disciplines still seem to be disconnected. This lack of integration between chemistry, engineering, and other key disciplines has been one of the main challenges that we have had within the industrial workplace and in previous academic experiences. As a consequence of these experiences, we decided to write this book to bridge the great divide between bench chemistry, process design, engineering, environment, health, safety, and life cycle considerations. We felt that a systems-oriented and integrated approach was needed to evolve green chemistry and green engineering as disciplines in the broader context of sustainability. To achieve this, we have organized the book in five main sections. xi

xii PREFACE. Part I. Green Chemistry and Green Engineering in the Movement Toward Sustainability. Chapters 1 to 4 set the broader context of sustainability, highlighting the key role that green chemistry and green engineering have in moving society toward the adoption of more sustainable practices in providing key items of commerce.. Part II. The Beginning: Designing Greener, Safer Chemical Synthesis. Chapters 5 to 8 address the key components of chemistry that will contribute to the achievement of more sustainable chemical reactions and reaction pathways. They also provide an approach to materials selection that promotes the overall greenness of a chemical synthesis without diminishing the efficiency of the chemistry or associated chemical process.. Part III. From the Flask to the Plant: Designing Greener, Safer, More Sustainable Manufacturing Processes. Chapters 9 to 15 provide those key engineering concepts that support the design of greener, more sustainable chemical processes.. Part IV. Expanding the Boundaries: Looking Beyond Our Processes. Chapters 16 to 20 introduce a life cycle thinking perspective by providing background and context for placing a particular chemical process in the broader chemical enterprise, including its impacts from raw materials extraction to recycle/reuse or end-of-life considerations.. Part V. What Lies Ahead: Beyond the Chemical Processing Technology of Today or Delivering Tomorrow s Products More Sustainably. Finally, Chapters 21 to 25 provide some indication of trends in chemical processing that may lead us toward more sustainable practices. To help provide a practical approach, we have included examples and exercises that will help the student or practitioner to understand these concepts as applied to the industrial setting and to use the material in direct and indirect applications. The exercises are intended to make the book suitable for both self-study or as a textbook, and most exercises are derived from our professional experiences. The book is an outgrowth of our experience in applied and fundamental research, consulting, teaching, and corporate work on the areas of green chemistry, green engineering, and sustainability. It is intended primarily for graduate and senior-level courses in chemistry and chemical engineering, although we believe that chemists and engineers working in manufacturing, research, and development, especially in the fine-chemical and pharmaceutical areas, will find the book to be a useful reference for process design and reengineering. Our aim is to provide a balance between academic needs and practical industrial applications of an integrated approach to green chemistry and green engineering in the context of sustainability. Acknowledgments We thank all our colleagues who have contributed directly or indirectly to our journey toward sustainability, and whose ideas and collaborations throughout the years have contributed to our own experience in the areas of green chemistry and green engineering. We also express our gratitude to GlaxoSmithKline, in general, and to James R. Hagan, in particular, for their support and encouragement.

PREFACE xiii We also give special thanks to Rafiqul Gani and Ana Carvalho from the Computer Aided Process-Product Engineering Center, Department of Chemical and Biochemical Engineering at the Technical University of Denmark, for their comments, reviews, and contributions to Chapter 12; to Mariana Pierobon and BASF for their helpful comments and for allowing us to use one of BASF s eco-efficiency assessments as an example in the life cycle chapters; to Sara Conradt for allowing us to use a sample of her masters thesis as an example of LCA outputs; and to Tom Roper and John Hayler at GSK for their feedback on green chemistry throughout the years. Finally, we want to thank Chemical Engineering magazine, the American Chemical Society, Springer Science and Business Media, Elsevier, John Wiley & Sons, the Royal Society of Chemistry, and Wiley-VCH for permission to reproduce some printed material. December 2009 CONCEPCIÓN JIMENEZ-GONZALEZ DAVID J. C. CONSTABLE