Concise Handbook of Fluorocarbon Gases: Applications in Refrigeration and Other Industries

This book describes fluorocarbons gases’ preparation process, properties, applications and their evolution over time.  The impact of fluorocarbons on the ozone layer and global and the development to mitigate those effects have been specially emphasized.  The first major industrial fluorinated compound was developed in the 1920’s, to replace ammonia and sulfur dioxide refrigerants, at the General Motors Frigidaire Division by Thomas Midgley, Jr. and Albert Leon Henne.  They developed a family of fluorocarbons trademarked Freon® for auto air conditioning units revolutionizing the auto industry.  Other applications were developed over time including fire extinguishers, propellants, blowing agents, cleaners, anesthesia, artificial blood and others impacting every facet of life. In spite of being in broad global use for nearly a century, fluorocarbon gases have gone through great evolution during the last few decades.  In the 1980s it was discovered chlorofluorocarbon (CFC) gases are harmful to the ozone layer, mainly because of their chlorine content.  Chlorine was released in the upper atmosphere when chlorofluorocarbon molecules were broken down by the high energy cosmic radiation. CFCs were progressively banned following the Montreal Protocol of 1987.  CFCs were replaced by fluorinated gases containing either less chlorine (hydrofluoro-chlorocarbons, or HCFCs), which are much less damaging (about 90% less) to the ozone layer or with fluorinated gases containing no chlorine, i.e. hydrofluorocarbons or HFCs. HFC have no impact on the ozone layer but impact global warming detrimentally.  HFCs are usable without need for changes to the existing refrigeration or air conditioning installations.  More recently hydrofluoroolefins (HFOs), which have little or no negative impact on global warming, have been developed to replace or reduce the use of HFCs.  HFOs are used as single compounds or in blends. Research and development continues to develop and replace the HCFCs and HFCs completely with environmentally friendly products. Concise Handbook of Fluorocarbon Gases presents a reference and text for the commercial fluorocarbon gases which have great many application in a wide range of industries such as refrigeration and air conditioning, as well as consumer products. 

Table of Contents:
Preface xi 1 Introduction 1 1.1 Terminology 1 1.2 Production and Consumption Statistics of Fluorocarbons 3 1.2.1 Refrigerants: Market Trends and Supply Chain Assessment 3 1.2.2 Fluorocarbon Consumption Demand 6 1.3 Production and Consumption Statistics of Fluoropolymers 7 1.4 Production and Consumption Statistics of Fluoroelastomers 9 1.5 Production and Consumption Statistics of Fluorinated Coatings 9 1.6 Specialty Fluorochemicals 10 References 10 2 Classification and Description of Commercial Fluorinated Compounds 13 2.1 Fluorine and Fluorochemicals 13 2.2 Fluorocarbons 13 2.3 Designations for Fluorocarbons 15 2.4 Fluoropolymers and Fluoroelastomers 22 2.4.1 Fluoropolymers 23 2.4.2 Fluoroelastomers 24 2.5 Fluorinated Coatings 26 2.6 Summary 27 References 27 3 Fluorine Sources and Basic Fluorocarbon Reactions 29 3.1 Role of Fluorine in Fluorocarbons 29 3.2 Fluorine Sources 30 3.3 Fluorocarbon Compounds 34 3.4 Hydrofluoric Acid 34 3.4.1 Manufacturing Hydrofluoric Acid 34 3.5 Aliphatic Fluorinated Organic Compounds 35 3.6 Synthesis of Fluorocarbons 36 References 38 4 Applications of Fluorocarbon Gases and Liquids 41 4.1 Refrigeration and Air Conditioning 41 4.1.1 Refrigeration Applications 46 4.1.1.1 Chillers 46 4.1.1.2 Cold Storage Warehouses 46 4.1.1.3 Commercial Ice Machines 47 4.1.1.4 Household Refrigerators and Freezers 47 4.1.1.5 Ice Skating Rinks 48 4.1.1.6 Industrial Process Air Conditioning 48 4.1.1.7 Industrial Process Refrigeration 48 4.1.1.8 Motor Vehicle Air Conditioning 48 4.1.1.9 Non-Mechanical Heat Transfer Systems 48 4.1.1.10 Residential and Light Commercial Air Conditioning and Heat Pumps 48 4.1.1.11 Residential Dehumidifiers 48 4.1.1.12 Refrigerated Transport 49 4.1.1.13 Retail Food Refrigeration 49 4.1.1.14 Vending Machines 49 4.1.1.15 Very Low Temperature Refrigeration 49 4.1.1.16 Water Coolers 49 4.2 Oil in Refrigerants 49 4.2.1 Oil Return 51 4.3 Monomers and Intermediates 51 4.4 Foam Blowing 52 4.4.1 Foam Blowing Agents 52 4.4.2 Foaming Process 54 4.4.3 Flexible Polyurethane Foams 59 4.5 Aerosol Propellants 60 4.6 Fire Extinguishing Agents 61 4.6.1 Aerospace Fire Extinguishing 63 4.7 Cleaning and Drying Solvents 66 4.8 Carrier Fluids/Lubricant Deposition 70 4.9 Heat Transfer 71 4.10 Etchants 72 4.10.1 What is Etching? 72 4.10.2 Fluorocarbon Etchants 72 4.11 Medical Applications 74 4.11.1 Enfluorane 76 4.11.2 Isoflurane 77 4.11.3 Desflurane 77 4.11.4 Sevoflurane 78 4.11.5 Methoxyflurane 79 4.12 Usage of HCFCs and HFCs 79 4.12.1 Introduction 80 4.13 Breakdown of Fluorocarbons in Applications 80 4.14 Summary 82 References 84 5 Refrigeration Cycle and Refrigerant Selection: How Refrigerant Gases Work? 87 5.1 Refrigeration Cycle 87 5.1.1 Reversed Carnot Cycle 89 5.1.2 Ideal Vapor-Compression Refrigeration Cycle 91 5.1.3 Actual Vapor-Compression Refrigeration Cycle 91 5.2 Selection of Right Refrigerant 92 5.3 Refrigerant Blends 95 5.4 Comparison of Refrigerator and Air Conditioning Systems 97 References 98 6 Preparation of Fluorocarbons 99 6.1 Introduction 99 6.2 Classification of Fluorocarbons 101 6.3 Preparation of Chlorofluorocarbons (CFCs) 104 6.3.1 Longevity of Process Catalysts 121 6.4 Fluorocarbon Replacements of CFCs 124 6.5 Substitutes for CFCs: HCFC and HFC 125 6.5.1 Preparation of Hydrochlorofluorocarbons (HCFCs) 126 6.5.2 Preparation of Hydrofluorocarbons (HFCs) 131 6.6 Preparation of Hydrofluoroolefins (HFOs) 142 6.7 Preparation Perfluorinated Alkanes 146 6.8 Summary 150 References 150 7 Properties of Fluorocarbons 155 8 Environmental, Safety, Health and Sustainability 217 8.1 Montreal Protocol 217 8.2 Ozone Depletion 224 8.3 Global Warming 230 8.3.1 Paris Agreement 233 8.4 Phase Out of Old Fluorocarbon Gases 234 8.4.1 Status of Phase Out of HCFCs 236 8.5 Summary 237 References 237 9 Fluorocarbon Blends 241 9.1 General Blend Characteristics 245 9.1.1 Azeotropic 245 9.1.2 Zeotropic Blends 245 9.2 Low GWP HFO and HFO/HFC Blends 251 9.3 Flammability of Blends 266 References 266 10 Substitute Fluorocarbons and Other Compounds 267 10.1 SNAP Program (EPA, www.epa.gov/snap/overview-snap) 267 10.2 Guiding Principles of the SNAP Program? 268 10.3 EPA’s Criteria for Evaluating Alternatives? 268 10.3.1 Atmospheric Effects 268 10.3.2 Exposure Assessments 268 10.3.3 Toxicity Data 269 10.3.4 Flammability 269 10.3.5 Other Environmental Impacts 269 10.4 Alternatives for Refrigeration 270 10.4.1 Chillers 270 10.4.2 Cold Storage Warehouses 270 10.4.3 Commercial Ice Machines 270 10.4.4 Household Refrigerators and Freezers 270 10.4.5 Ice Skating Rinks 270 10.4.6 Industrial Process Refrigeration 273 10.4.7 Refrigerated Transport 273 10.4.8 Retail Food Refrigeration 273 10.4.9 Vending Machines 273 10.4.10 Very Low Temperature Refrigeration 273 10.4.11 Water Coolers 273 10.5 Alternatives for Air Conditioning 273 10.5.1 Industrial Process Air Conditioning 273 10.5.2 Motor Vehicle Air Conditioning 279 10.5.3 Non-Mechanical Heat Transfer Systems 279 10.5.4 Residential and Light Commercial Air Conditioning and Heat Pumps 279 10.5.5 Residential Dehumidifiers 279 11 Future Directions of Fluorocarbons 283 11.1 Introduction 283 11.2 Inception and Evolution of Fluorocarbons 284 11.3 Classification of Refrigerants 286 11.3.1 First Generation (Prior to 1930) 286 11.3.2 Second Generation (1931–1990) 288 11.3.3 Third Generation (1990–2010) 288 11.3.4 Fourth Generation (Beyond 2010) 289 11.3.5 Hydrofluoroolefin Fluorocarbons 291 11.4 Natural Refrigerants 296 11.4.1 Carbon Dioxide 299 11.4.2 Hydrocarbons 306 11.4.3 Ammonia 306 11.5 Phase Out of Fluorocarbon Gases 306 11.6 Future Directions of Refrigerants 309 11.6.1 Introduction 309 11.6.2 Towards the Future 309 11.6.2.1 Innovation 310 11.6.2.2 Innovation Accelerating Transition 310 11.6.2.3 Speed Bumps 310 11.6.2.4 New Developments 312 11.7 Conclusions 313 References 313 Appendix I 317 Appendix II 373 Appendix III 381 Index 403