Sustainable Industrial Chemistry

Professor Fabrizio Cavani received his PhD in Industrial Chemistry from the University of Bologna in 1986. From 1986 to 1990 he worked at the Catalysis Centre of EniChem, where he investigated new catalysts for the oxychlorination of ethylene and for the Alkylation of benzene with propene, and gave technical assistance to the catalysts production division. In 1990 he joined the Catalytic Processes Development team at the University of Bologna becoming Associate Professor of Industrial Chemistry there in 2000. Hee is author of over 200 journal articles, 25 patents, two books on catalytic selective oxidation and one book on the development and management of chemical processes and is the editor of 4 special journal issues. he is on the board of the Italian Platform for Sustainable Chemistry.Professor Gabriele Centi is Full Professor of Industrial Chemistry at the University of Messina and a past President of the European Federation of Catalysis Societies. He is the Coordinator of the Network of Excellence IDECAT and Co-Director of the European Laboratory for Catalysis and Surface Science and President of ERIC (European Research Institute of Catalysis). His research activities lie in the development of industrial heterogeneous catalysts for the field of sustainable chemical processes, environmental protection and clean energy. He is author of over 260 journal articles, editor and/or author of 7 books, editor of 7 special issues, chairman of several International Congresses and Editor of the Wiley-VCH journal ChemSusChem. He is also a Core Team member for the European Technology Platform for Sustainable Chemistry.Professor Siglinda Perathoner is Associate Professor of Industrial Chemistry at the University of Messina. After some years experience in the field of photophysics and photochemistry of supramolecular systems, she moved to the area of catalysts. In 2001 she joined the University of Messina where her most recent research interest include nanostructured zeolites, catalytic membranes, catalysts for reactions in supercritical fluids, catalysts for waste water purification and remediation, photo(electro)catalytic conversion of carbon dioxide, and fuel cells. Her aim is the design of novel catalytic materials for sustainable processes, environment protection, and cleaner energy. She is author of over 130 publications, including 15 reviews, has been co-editor of a book and two special journal issues, and has contributed to various entries in encyclopedias.Professor Ferruccio Trifiró is Full Professor of Industrial Chemistry at the University of Bologna. Currently he is the Dean of the Faculty of Industrial Chemistry, and Director of the journal La Chimica e L'Industria (Chemistry and Industry). His main research activities lie in the development of heterogeneous catalysts for processes in the field of petrochemistry, environmental protection, fine chemicals and specialties production, clean energy and hydrogen production. He is a past Chairman of the World Congress of Selective Oxidation. He is author of over 300 papers in International Journals, two books on Selective Oxidation, and of 18 patents.

• Preface XVList of Contributors XIX1 From Green to Sustainable Industrial Chemistry 1Gabriele Centi and Siglinda Perathoner1.1 Introduction 11.2 Principles of Green Chemistry, Sustainable Chemistry and Risk 111.3 Sustainable Chemical Production and REACH 361.4 International Chemicals Policy and Sustainability 431.5 Sustainable Chemistry and Inherently Safer Design 471.6 A Vision and Roadmap for Sustainability Through Chemistry 561.7 Conclusions 692 Methods and Tools of Sustainable Industrial Chemistry: Catalysis 73Gabriele Centi and Siglinda Perathoner2.1 Introduction 732.2 Catalysis as Enabling Factor of Sustainable Chemical Production 742.3 Homogeneous Catalysis and the Role of Multiphase Operations 772.4 Bio- and Bioinspired-Catalysts 1032.5 Solid Acids and Bases 1202.6 Redox Catalysis 1582.7 Cascade and Domino Catalytic Reactions 1842.8 Multicomponent Catalytic Reactions 1862.9 Organocatalysis 1872.10 Conclusions 1883 Methods and Tools of Sustainable Industrial Chemistry: Process Intensification 199Gabriele Centi and Siglinda Perathoner3.1 Introduction 1993.2 Alternative Sources and Forms of Energy for Process Intensification 2303.3 Micro(structured)-Reactors 2434 Membrane Technologies at the Service of Sustainable Development Through Process Intensification 257Gilbert M. Rios, Marie-Pierre Belleville, Delphine Paolucci-Jeanjean, and José Sanchez4.1 Introduction 2574.2 From Definitions to Function: A Few Fundamental Ideas 2584.3 The Need for More Integrated Views on Materials and Process Conditions 2624.4 Use of Hybrid Processes and New Operating Modes: The Key to Many Problems 2674.5 Safe Management of Membrane Integration in Industrial Processes: A Huge Challenge 2734.6 Conclusions 2765 Accounting for Chemical Sustainability 279Gabriele Centi and Siglinda Perathoner5.1 Introduction 2795.2 Ecological Footprint 2815.3 Ecological Indicators 2835.4 Metrics for Environmental Analysis and Eco-Efficiency 2835.5 Sustainability Accounting 2925.6 E-Factor and Atom Economy 2965.7 Energy Intensity 3045.8 Environmental Impact Indicators 3055.9 Sustainable Chemical Production Metrics 3065.10 Life Cycle Tools 3105.11 Conclusions 3156 Synthesis of Propene Oxide: A Successful Example of Sustainable Industrial Chemistry 319Fabrizio Cavani and Anne M. Gaffney6.1 Introduction: Current Industrial Propene Oxide Production 3196.2 PO-only Routes: Several Approaches for Sustainable Alternatives 3236.3 Conclusions 3587 Synthesis of Adipic Acid: On the Way to More Sustainable Production 367Fabrizio Cavani and Stefano Alini7.1 Introduction: The Adipic Acid Market 3677.2 Current Technologies for AA Production 3687.3 Alternatives for AA Production 3857.4 Emerging and Developing Technologies for AA Production 4027.5 An Overview: Several Possible Green Routes to AA, Some Sustainable, Others Not 4138 Ecofining: New Process for Green Diesel Production from Vegetable Oil 427Franco Baldiraghi, Marco Di Stanislao, Giovanni Faraci, Carlo Perego, Terry Marker, Chris Gosling, Peter Kokayeff, Tom Kalnes, and Rich Marinangeli8.1 Introduction 4278.2 From Vegetable Oil to Green Diesel 4288.3 UOP/Eni Ecofining Process 4348.4 Life Cycle Assessment 4358.5 Conclusion 4379 A New Process for the Production of Biodiesel by Transesterification of Vegetable Oils with Heterogeneous Catalysis 439Edouard Freund9.1 Introduction 4399.2 Direct Use of Vegetable Oils 4419.3 Methyl Ester Derived from Vegetable Oils 4419.4 Homogeneous Process for the Production of Biodiesel 4429.5 Improving the Transesterification Route: Esterfip-H 4459.6 Future Improvements of the Process 4479.7 Conclusion 44810 Highly Sour Gas Processing in a More Sustainable World 449François Lallemand and Ari Minkkinen10.1 Introduction 44910.2 Use of Activated MDEA for Acid Gas Removal 45110.3 Process Performance Highlights 45410.4 Case Study of the Use of Activated MDEA for Treatment of Very Sour Gas 45410.5 Acid Gas Removal for Cycling and/or Disposal 45610.6 Bulk H2S Removal for Disposal 45810.7 SPREX Performance 45910.8 Capital Cost and Energy Balance Comparison 46010.9 Conclusions 46111 BioETBE: A New Component for Gasoline 463Marco Di Girolamo and Domenico Sanfilippo11.1 Introduction 46311.2 High Quality Oxygenated as Gasoline Components 46311.3 ETBE Technology 46612 Olefin/Paraffin Alkylation: Evolution of a "Green" Technology 475Anne M. Gaffney and Philip J. Angevine12.1 Introduction 47512.2 Liquid Acid Catalysts 47612.3 Zeolite Catalysts 48412.4 AlkyClean Alkylation Process: A True Solid Acid Catalyst (SAC) Process 48812.5 Conclusion 50413 Towards the Direct Oxidation of Benzene to Phenol 507Marco Ricci, Daniele Bianchi, and Rossella Bortolo13.1 Introduction 50713.2 Cumene Process 50813.3 Solutia Process 51413.4 Direct Oxidation of Benzene to Phenol with Hydrogen Peroxide 51613.5 Perspectives 52513.6 Conclusions 52514 Friedel-Crafts Acylation of Aromatic Ethers Using Zeolites 529Roland Jacquot and Philippe Marion14.1 Introduction 52914.2 Literature Background 53014.3 Acylation of Anisole by Acetic Anhydride 53014.3.1 Industrial Processes 53114.4 Acylation of Veratrole by Acetic Anhydride Over HY Zeolite 53314.5 Deactivation of the Catalysts 53414.6 Benzoylation of Phenol Ether 53614.7 Concluding Remarks 53915 Green Sustainable Chemistry in the Production of Nicotinates 541Roderick Chuck15.1 Requirements for Green Processes 54115.2 Significance of Niacin 54215.3 Green Principles in the Manufacture of Niacin 54215.4 Green Principles in Lonza's Niacinamide Process (5000 mtpa) 54816 Introducing Green Metrics Early in Process Development. Comparative Assessment of Alternative Industrial Routes to Elliott's Alcohol, A Key Intermediate in the Production of Resmethrins 551Paolo Righi, Goffredo Rosini, and Valerio Borzatta16.1 Introduction 55116.2 Elliott's Alcohol 55216.3 An Alternative Synthesis of Elliott's Alcohol 55416.4 Comparative Assessment of the Two Alternative Routes to Elliott's Alcohol 55516.5 Driving the "Green" Improvement 56116.6 Conclusions 56117 Basell Spherizone Technology 563Maurizio Dorini and Gabriele Mei17.1 Introduction 56317.2 Technology Evolution 56317.3 Spherizone Technology 56717.4 Technology Comparison 57517.5 Environmental Considerations 576References 578Index 579