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
10.2 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
