Gas Engineering: Vol. 3: Uses of Gas and Effects 9783110691016, 9783110690910

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James G. Speight Gas Engineering

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James G. Speight

Gas Engineering

Vol. 3: Uses of Gas and Effects

Author Dr. James G. Speight 2476 Overland Road Laramie 82070-4808 USA [email protected]

ISBN 978-3-11-069091-0 e-ISBN (PDF) 978-3-11-069101-6 e-ISBN (EPUB) 978-3-11-069111-5 Library of Congress Control Number: 2023931071 Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.dnb.de. © 2023 Walter de Gruyter GmbH, Berlin/Boston Cover image: nielubieklonu/iStock/Getty Images Plus Typesetting: Integra Software Services Pvt. Ltd. Printing and binding: CPI books GmbH, Leck www.degruyter.com

Preface The final three decades of the twentieth century and the first two decades of the twenty-first century have experienced not only perturbations of energy supply systems but also changes in attitudes of governments and voters alike toward environmental issues. Thus, environmental issues will be with us as long as there is manufacturing of e-consumer goods and the use of fossil fuels for energy production. And it is this latter issue that is the subject of this text. The continued use of gas streams as combustible fuel is a reality, and gas processing, although generally understandable using chemical and/or physical principles, still requires an attempt to alleviate some of the confusion that arises from uncertainties in the terminology. However, while gas streams (particularly natural gas) offer options for the production of energy and chemicals, there are issues that need to be addressed before use of any of the various gas areas. This three-volume collection of books presents to the reader an understanding of the origin of gases, the properties of gases, and the uses of gases. The primary aim of the first volume was to introduce the reader to the origins of natural gas, and it contains chapters dealing with recovery, properties, and composition, including gas production from hydrocarbon-rich deep shale formations, known as shale gas, which is one of the most quickly expanding trends in onshore domestic gas exploration, and presents the development of deep shale formations, typically located many thousands of feet below the surface of the Earth in tight, low-permeability formations. The basic technology of reservoir engineering is presented using the simplest and most straightforward of mathematical techniques. The book focuses processes and, wherever possible, the advantages, limitations, and ranges of applicability of the processes are discussed so that the selection and integration into the overall gas plant can be fully understood. It is only through having a complete understanding of the technology that the engineer can hope to appreciate and solve complex reservoir engineering problems in a practical manner. Volume 2 deals with the constituents of gas streams and the properties of the individual constituents. The volume also presented the chemistry and engineering aspects of the methods and principles by which the gas streams might be cleaned from their noxious constituents. The concept of gas condensate is also introduced and discussed as well as the methods which can be applied to the analysis of gas streams and gas condensate. The second volume also contains references to several other types of gas streams (in addition to the subcategories of natural gas) that need to be presented her and include the following gas streams that are listed alphabetically rather than by any order of importance: (1) refinery gas, (2) biogas, (3) coalbed methane, (4) coal gas, of which there are various types, (5) flue gas, (6) landfill gas, (7) shale gas, and (8) synthesis gas all of which will, more than likely, also require processing for the removal of contaminants. If these gas stream are not already co-processed with natural gas, there

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Preface

is the expectation that as the future unfolds, such gas stream will evolve and become more common to the gas industry. Volume 3 introduces the concept of liquefied natural gas and the concept “gas to liquids” and also presents a review of the uses of gas streams and the effects of the various gases on the environment. This volume also describes the properties gas streams, and the way they are related to corrosion effects is also presented. The relationship of the properties of gas streams as they affect corrosion such as carburization and metal dusting as well as corrosion in steel and other materials used in refinery technology is also presented, and the book summarizes key findings into corrosion processes in gas-processing equipment as well as corrosion in offshore structures. Each book contains references at the end of chapter which include information from the open literature and meeting proceedings to give a picture of where the gas processing technology stands as well as indicate some relatively new technologies that could become important in the future. Also, each book contains a comprehensive glossary. The books are written in an easy-to-read style and offer a ready-at-hand (one-stopshopping) guide to the many issues that are related to the engineering aspects of the properties and processing of natural gas as well as the effects of natural gas on various ecosystems as well as to pollutant mitigation and cleanup. The books present an overview with a considerable degree of detail of the various aspects of natural gas technology. Any chemistry presented in the books is used as a means of explanation of a particular point but is maintained at an elementary level. Dr. James G. Speight, Laramie, Wyoming, USA January 2023

Contents Preface

V

Chapter 1 Types and properties of gas streams 1 1.1 Introduction 1 1.2 Types of gas streams 2 1.2.1 Biogas 2 1.2.2 Coalbed methane 6 1.2.3 Coal gas 7 1.2.4 Flue gas 11 1.2.5 Landfill gas 14 1.2.6 Natural gas 16 1.2.7 Refinery gas 22 1.2.8 Synthesis gas 27 1.3 Constituents of gas streams 28 1.3.1 Methane 31 1.3.2 Ethane 32 1.3.3 Propane 33 1.3.4 Butane 33 1.3.5 Olefin derivatives 34 1.3.6 Higher molecular weight hydrocarbon derivatives 1.3.7 Non-hydrocarbon constituents 36 1.4 Chemical and physical properties 37 1.4.1 Chemical properties 41 1.4.2 Physical properties 46 1.5 Uses 48 References 54 Chapter 2 Liquefaction of gases 59 2.1 Introduction 59 2.2 The liquefaction process 63 2.2.1 The refrigeration cycle 69 2.2.2 The evaporation step 70 2.2.3 The compression step 71 2.2.4 The condensation step 72 2.3 Processes 73 2.4 Storage and transfer facilities 2.4.1 General requirements 84 2.4.2 Specific requirements 86

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2.4.2.1 2.4.2.2 2.4.2.3 2.4.2.4 2.4.2.5 2.4.2.6 2.4.2.7 2.5 2.6

Contents

Cryogenic process system 87 Pumps and compressors 88 Storage tanks 88 Insulation 89 Relief devices 89 Instrumentation 89 Other requirements 90 Liquefied natural gas carriers 91 Liquefied petroleum gas 94 References 95

Chapter 3 Combustion of gases 97 3.1 Introduction 97 3.2 History of combustion 99 3.3 Combustion fundamentals 102 3.3.1 Combustion chemistry of gases 105 3.3.2 Flammability and flame propagation 112 3.3.3 Combustion products and pollutants 113 3.4 Gaseous fuels 113 3.4.1 Natural gas 114 3.4.2 Hydrogen 115 3.4.3 Methane 117 3.4.4 Ethane 117 3.4.5 Propane 118 3.4.6 Butane 118 3.4.7 Liquefied petroleum gas 119 3.5 Combustion processes and combustors 121 3.5.1 Types of combustors 124 3.5.2 Ignition system 128 3.5.3 Furnace 128 3.5.4 Boiler 128 3.5.5 Ash-handling system 130 3.5.6 Flue-gas stack 130 3.6 Gaseous fuel combustion systems 131 3.6.1 Gas engine 131 3.6.2 Gas turbine 131 3.7 Power generation 132 3.7.1 Thermal power plants 132 3.7.2 Cogeneration (combined heat and power) 132 3.7.3 Trigeneration 133 3.7.4 Combined cycle 133

Contents

3.8 3.8.1 3.8.2 3.8.2.1 3.8.2.2 3.8.2.3 3.8.3 3.8.3.1 3.8.3.2 3.8.3.3 3.8.4 3.8.4.1 3.8.4.2

Combustion diagnostics and control 134 Diagnostics 134 Advanced combustion control 135 Safety 135 Fire prevention 135 Explosion prevention 136 Combustion emissions and controls 138 Emissions 138 Greenhouse gases 141 Controls 142 Pollutant reduction and flue-gas cleaning 144 Greenhouse gas emissions 145 Smog and acid rain 146 References 147

Chapter 4 Conversion of gases to liquids 149 4.1 Introduction 149 4.2 Occurrence, resources, and properties 4.2.1 Non-associated gas 153 4.2.2 Associated gas 154 4.2.3 Composition 155 4.2.4 Natural gas liquids 156 4.2.5 Other gas streams 156 4.3 Processes 157 4.3.1 Direct conversion of methane 159 4.3.2 Synthesis gas production 161 4.3.3 Gas to methanol 164 4.3.4 Gas to dimethyl ether 166 4.3.5 Gas to olefins 167 4.3.6 Gas to naphtha (gasoline) 168 4.3.7 Fischer–Tropsch process 169 4.3.7.1 Process description 170 4.3.7.2 Chemistry 171 4.3.7.3 Products 173 4.3.7.4 Catalysts 174 4.3.7.5 Commercial processes 174 4.3.8 Other processes 178 4.4 The future 180 References 181

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Chapter 5 Conversion of gases to chemicals 184 5.1 Introduction 184 5.2 Thermal reactions 186 5.2.1 Thermal decomposition 188 5.2.2 Steam cracking 192 5.3 Catalyst-promoted reactions 195 5.3.1 Fluid catalytic cracking 197 5.3.2 Hydrocracking 198 5.3.3 Catalytic reforming 200 5.4 Hydrogenation reactions 201 5.5 Dehydrogenation reactions 204 5.6 Dehydrocyclization reactions 207 5.7 Chemical reactions 209 5.7.1 Alkylation 210 5.7.2 Halogenation 211 5.7.3 Hydration 213 5.7.4 Oxidation 213 5.7.5 Polymerization 214 5.7.6 Rearrangement 215 5.7.7 Substitution 215 5.8 Organic petrochemicals from gases 5.8.1 Chemicals from methane 218 5.8.1.1 Acetic acid 223 5.8.1.2 Aldehyde derivatives 223 5.8.1.3 Carbon disulfide 224 5.8.1.4 Chloromethane derivatives 224 5.8.1.5 Dimethyl carbonate 227 5.8.1.6 Dimethyl ether 227 5.8.1.7 Ethylene 228 5.8.1.8 Ethylene glycol 229 5.8.1.9 Formaldehyde 230 5.8.1.10 Hydrocarbon derivatives 231 5.8.1.11 Hydrogen cyanide 234 5.8.1.12 Methyl alcohol 234 5.8.1.13 Methylamine 237 5.8.1.14 Nitro derivatives 238 5.8.1.15 Urea 238 5.8.2 Chemicals from ethane 239 5.8.2.1 Chlorination 240 5.8.2.2 Oxidation 241 5.8.2.3 Thermal cracking 242

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5.8.3 5.8.3.1 5.8.3.2 5.8.3.3 5.8.4 5.8.4.1 5.8.4.2 5.8.4.3 5.8.4.4 5.9

Chemicals from propane 242 Chlorination 243 Dehydrogenation 243 Nitration 244 Chemicals from butane isomers Aromatic derivatives 245 Chlorination 246 Isomerization 247 Oxidation 247 Inorganic chemicals from gases References 255

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Chapter 6 The Fischer–Tropsch process 258 6.1 Introduction 258 6.2 History and development of the process 262 6.3 Fischer–Tropsch chemistry 265 6.3.1 Chemical principles 265 6.4 Synthesis gas 271 6.4.1 Feedstocks 272 6.4.2 Production 276 6.4.3 Properties 278 6.4.4 Product distribution 279 6.5 Process parameters 283 6.6 Reactors and catalysts 285 6.6.1 Reactors 285 6.6.2 Catalysts 288 6.7 Products and product quality 291 6.7.1 Gases 292 6.7.2 Liquids 295 6.8 Refining Fischer–Tropsch products 296 References 298 Chapter 7 Corrosion caused by gases 300 7.1 Introduction 300 7.2 Corrosion chemistry 301 7.2.1 General chemistry 302 7.2.2 Anodic reactions 303 7.2.3 Cathodic reactions 304 7.3 Types of corrosion 304 7.3.1 Acidic corrosion 305

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7.3.2 7.3.2.1 7.3.2.2 7.3.3 7.3.4 7.3.5 7.3.6 7.3.7 7.3.8 7.3.9 7.3.10 7.3.11 7.3.12 7.4 7.5 7.5.1 7.5.2 7.5.3 7.6 7.6.1 7.6.2 7.6.3 7.6.3.1 7.6.3.2 7.6.4 7.6.5 7.7 7.7.1 7.7.2 7.7.3 7.7.4 7.7.5 7.7.6 7.7.6.1 7.7.6.2 7.7.6.3 7.7.6.4 7.7.6.5 7.8 7.8.1 7.8.2 7.8.3

Contents

Atmospheric corrosion 305 Dry corrosion 306 Wet corrosion 306 Biocorrosion 307 Carburization 308 Crevice corrosion 308 De-alloying 309 Erosion–corrosion 309 Hydrogen damage 310 Oxidative corrosion 310 Sour water corrosion 311 Sulfidic corrosion 312 Uniform and localized corrosion 313 Effect of temperature 314 Corrosion during gas processing and use 315 Corrosion by hydrogen sulfide 320 Corrosion by carbon dioxide 324 Other corrosive agents 324 Inhibition of corrosion 325 Acid gas removal 326 Sour water stripper 328 Sulfur recovery units 328 Claus process 329 Other units 330 Acid gas flare header 331 Heat exchangers 331 Corrosion monitoring 332 Corrosion coupons 333 Electrical resistance methods 334 Field signature methods 335 Linear polarization resistance monitoring 335 Galvanic monitoring 336 Other methods 336 Iron powder test 336 Hydrogen penetration monitoring 337 Radiography 337 Biological monitoring 337 Sand/erosion monitoring 337 Corrosion control in gas processing plants 338 Cathodic protection 339 Galvanic cathodic protection 340 Impressed current cathodic protection 340

Contents

7.8.4 7.9 7.9.1 7.9.2 7.10 7.10.1 7.10.2 7.10.3 7.10.4 7.11

Cathodic shielding 341 Corrosion control in pipelines 341 Protective coatings 342 Cathodic protection 342 Corrosion control in offshore structures Hull components 344 Tanks 345 Riser systems 346 Miscellaneous areas 346 Corrosion management 347 References 349

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Chapter 8 Gases and the environment 353 8.1 Introduction 353 8.2 Energy security 357 8.2.1 Reserves 357 8.2.2 Energy security 358 8.3 Emissions and pollution 359 8.3.1 Greenhouse gas emissions 362 8.3.2 Air pollutants 365 8.3.2.1 Emissions during exploration, production, and delivery 8.3.2.2 Emissions during processing 371 8.3.2.3 Emissions during combustion 372 8.3.2.4 Emissions during flaring 374 8.4 Acid rain and smog 375 8.5 Particulate matter 377 8.6 Regulations 378 8.6.1 Historical aspects 379 8.6.2 Federal regulations 383 8.7 Pollution mitigation 385 References 386 Glossary

389

Conversion factors and constants 449 1 Area 449 2 Compressibility factor 449 3 Concentration conversion 450 4 Density 450 5 Conversion 451 6 Gas constant 452

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7 8 9 10 11 12 13 14 15 16

Contents

Length conversion 453 Periodic table of the elements 454 Pressure unit conversion factors 454 Sludge conversion 454 Standard gas conditions 455 Temperature conversion 455 Thermodynamic data at 25 °C for selected constituents of natural gas 455 Weight conversion 456 Volume conversion 456 Other conversions 456

About the author Index

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Chapter 1 Types and properties of gas streams 1.1 Introduction By definition, as identified for the purposes of this book, gas streams contain varying amounts of hydrocarbon derivatives as well as varying amounts of non-hydrocarbon constituents of which the corrosive acid gases such as hydrogen sulfide and carbon dioxide are examples and which, along with any other acidic constituents, can result in a high potential for the corrosion of equipment (Chapter 7) [1, 2]. Thus, in order to understand the effects of gas streams, a brief review of the types and properties of the various types of gases is warranted here. Although presented in more detail elsewhere in this book series [3], the review presented here is necessary and will be convenient in terms of the context of this current volume (Volume 3 of this Gas Engineering Series) and will give the reader the necessary easy access to the more detailed data. Although the terminology and definitions involved in the area of gas technology are quite succinct but numerous, there may be those readers that find the terminology and definitions somewhat confusing. Briefly, terminology is the means by which various subjects are named so that reference can be made in conversations and in writings and so that the meaning is passed on. On the other hand, definitions are the means by which scientists and engineers communicate the nature of a material to each other either through the spoken or through the written word. Thus, the terminology and definitions applied to the various gas streams are extremely important and have a profound influence on the manner by the gas streams can be characterized. For the purposes of this book, gas streams (as well as any products that are isolated from natural gas during the recovery operations) are not included in this text. Nevertheless, whatever, the source or origin, of the gas streams, they are already becoming important components of energy supply as well as the supply of other products (such as chemicals) as part of the necessary supply chain [Speight, 2014a, 3–5]: for the production of a variety of chemicals [4]: Source ! produced gas ! recovered gas ! transported gas Transported gas ! stored gas ! sales gas Transported gas ! stored gas ! chemicals From a chemical standpoint, the various gas streams are mixtures of a variety of constituents such as hydrocarbon derivatives and non-hydrocarbon compounds [2, 3, 6–8]. The more efficient use of these various gas streams gas in the production of energy and chemicals is of paramount importance, and the technology involved in processing https://doi.org/10.1515/9783110691016-001

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Chapter 1 Types and properties of gas streams

natural gas (and crude oil) will supply the industrialized nations of the world for (at least) the next five decades until suitable alternative forms of energy and chemicals (such as biogas and other non-hydrocarbon gases) are readily available [9–15]. Any gas sold, however, to an industrial or domestic consumer must meet designated specifications that are designed according to the use of the gas. In this chapter, the various sources of gas streams are presented as well as the limitations and potential of these sources are discussed. The technological and commercial challenges to be overcome in taking the world through the transition are identified. Finally alternatives to natural gas in both utilization and environmental concerns are also addressed. Thus, it is the purpose of this chapter to present the various types of gas streams in alphabetical order rather than in any order of importance or preference. Other non-petroliferous gas streams (often referred to as unconventional gas streams) are (in the context of this book) gas streams that are from sources that are, in a given era and location, considered to be new and different.

1.2 Types of gas streams The term “unconventional gas” does not describe the gas itself but refers to the sources from which the gas is obtained. In addition, unconventional gas also can include gas that is produced or extracted using techniques other than the conventional methods of extraction and production. Thus in the context of this book, the various gas streams are presented in the following order and include (1) biogas, (2) coalbed methane, (3) coal gas, (4) flue gas, (5) landfill gas, (6) natural gas, (7) shale gas, and (8) synthesis gas.

1.2.1 Biogas As the need for the replacement of fossil fuels as energy sources (especially as sources of gaseous fuels and gases for the production of petrochemicals) continues to grow, gaseous products from other sources (such as biomass) will continue to increase in importance. In fact, there are projections which indicate that biomass will play an increasingly important role not only in the future global energy infrastructure (for the generation of power and heat) but also in the future global chemical energy infrastructure (for the production of gaseous and liquid products as feedstocks for the chemical industry). Biomass is a source of alternative energy insofar as it can be used for fuel substitution and chemical production and (unlike the fossil fuels sources) is also a non-depleted resource which can be renewed and on an annual basis. As of the current production of energy and chemicals, the dominant gaseous processes for biomass conversion that are likely to be predominant in future conversion

1.2 Types of gas streams

3

processes will be (1) the gaseous products from anaerobic digestion processes, (2) the gas gaseous products from landfill sites, which will be of considerable interest when the amount of waste generated each year by various countries is given consideration, (3) the gaseous products from the thermal decomposition processes, commonly referred to as the pyrolysis of biomass, (4) the gaseous products from refineries, commonly known as “refinery gas” or “process gas”, and (5) any combination of two or more of the above processes. Furthermore, in the discussion of the production of gases from the various sources, it is important to understand that the composition of the produced gas is very dependent on the type of gas-producing process and especially the process parameters such as the composition of the source material, and the process parameters such as the temperature, the pressure, and the residence time of the source material in the hot zone which will dictate the predominance of the types of the reactions that produce the gases [8, 15–21]. More specifically in the current context, biogas (often called biogenic gas and sometimes incorrectly known as swamp gas) typically refers to a biofuel gas produced by (1) anaerobic digestion with anaerobic organisms, which digest material inside a closed system or (2) fermentation of biodegradable organic matter including manure, sewage sludge, municipal solid waste, biodegradable waste, or any other biodegradable feedstock, under anaerobic conditions (Table 1.1; Figure 1.1) [14, 22, 23]. Table 1.1: Variation in the composition of biogas (including landfill gas) from different sources✶. Constituents

Range

Methane, CH % v/v Carbon dioxide, CO % v/v Hydrogen, H % v/v Nitrogen, N % v/v Oxygen, O % v/v Water, HO % v/v (@  °C,  °F) Hydrogen sulfide,✶ HS mg/m Ammonia,✶ NH mg/m Chlorine, ppm v/v

– –