Petroleum Refining Design and Applications Handbook, Volume 1
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Kayode Coker PhD, is Engineering Consultant for AKC Technology, an Honorary Research Fellow at the University of Wolverhampton, U.K., a former Engineering Coordinator at Saudi Aramco Shell Refinery Company and Chairman of the department of Chemical Engineering Technology at Jubail Industrial College, Saudi Arabia. He has been a chartered chemical engineer for more than 30 years. He is a Fellow of the Institution of Chemical Engineers, U.K. and a senior member of the American Institute of Chemical Engineers. He holds a B.Sc. honors degree in Chemical Engineering, a Master of Science degree in Process Analysis and Development and Ph.D. in Chemical Engineering, all from Aston University, Birmingham, U.K. and a Teacher's Certificate in Education at the University of London, U.K. He has directed and conducted short courses extensively throughout the world and has been a lecturer at the university level. His articles have been published in several international journals. He is an author of five books in chemical engineering, a contributor to the Encyclopedia of Chemical Processing and Design. Vol 61. He was named as one of the International Biographical Centre's Leading Engineers of the World for 2008. Also, he is a member of International Who's Who of ProfessionalsTM and Madison Who's Who in the U.S.
Content
Preface xix
Acknowledgments xxi
About the Author xxiii
1 Introduction 1
References 6
2 Composition of Crude Oils and Petroleum Products 7
2.1 Hydrocarbons 8
2.1.1 Alkynes Series 12
2.2 Aromatic Hydrocarbons 14
2.3 Heteroatomic Organic Compounds 15
2.3.1 Non-Hydrocarbons 15
2.3.2 Sulfur Compounds 18
2.4 Thiols 18
2.5 Oxygen Compounds 20
2.6 Nitrogen Compounds 22
2.7 Resins and Asphaltenes 23
2.8 Salts 24
2.9 Carbon Dioxide 24
2.10 Metallic Compounds 24
2.11 Products Composition 25
2.11.1 Liquefied Petroleum Gas (LPG) (C3 and C4) 26
2.11.2 Gasoline (C5 to C11) 26
2.11.3 Condensate (C4, C5 and C6 >) 27
2.11.4 Gas Fuel Oils (C12 to C19) 27
2.11.5 Kerosene 27
2.11.6 Diesel Fuel 28
2.11.7 Fuel Oils # 4, 5, and 6 28
2.11.8 Residual Fuel Oil 28
2.11.9 Natural Gas 29
References 30
3 Characterization of Petroleum and Petroleum Fractions 31
3.1 Introduction 31
3.2 Crude Oil Assay Data 37
3.3 Crude Cutting Analysis 37
3.4 Crude Oil Blending 37
3.5 Laboratory Testing of Crude Oils 46
3.6 Octanes 58
3.7 Cetanes 58
3.7.1 Cetane Index 59
3.8 Diesel Index 59
3.9 Determination of the Lower Heating Value of Petroleum Fractions 59
3.10 Aniline Point Blending 60
3.11 Correlation Index (CI) 60
3.12 Chromatographically Simulated Distillations 61
References 624 Thermodynamic Properties of Petroleum and Petroleum Fractions 63
4.1 K-Factor Hydrocarbon Equilibrium Charts 64
4.2 Non-Ideal Systems 72
4.3 Vapor Pressure 74
4.4 Viscosity 80
4.5 Refractive Index 87
4.6 Liquid Density 89
4.7 Molecular Weight 90
4.8 Molecular Type Composition 90
4.9 Critical Temperature, Tc 96
4.10 Critical Pressure, Pc 97
4.11 Pseudo-Critical Constants and Acentric Factors 98
4.12 Enthalpy of Petroleum Fractions 99
4.13 Compressibility Z Factor of Natural Gases 100
4.14 Simulation Thermodynamic Software Programs 105
References 110
5 Process Descriptions of Refinery Processes 111
5.1 Introduction 111
5.2 Refinery and Distillation Processes 115
5.3 Process Description of the Crude Distillation Unit 120
5.4 Process Variables in the Design of Crude Distillation Column 132
5.5 Process Simulation 134
5.6 Process Description of Light Arabian Crude Using UniSim® Simulation Software [12] 138
5.7 Troubleshooting Actual Columns 144
5.8 Health, Safety and Environment Considerations 145
References 148
6 Thermal Cracking Processes 149
6.1 Process Description 152
6.2 Steam Jet Ejector 152
6.3 Pressure Survey in a Vacuum Column 154
6.4 Simulation of Vacuum Distillation Unit 156
6.5 Coking 157
6.6 Fluid Coking 164
6.7 Fractionator Overhead System 170
6.8 Coke Drum Operations 172
6.9 Hydraulic Jet Decoking 173
6.10 Uses of Petroleum Coke 174
6.11 Use of Gasification 174
6.12 Sponge Coke 175
6.13 Safety and Environmental Considerations 175
6.14 Simulation/Calculations 176
6.15 Visbreaking 177
6.16 Process Simulation 184
6.17 Health, Safety and Environment Considerations 185
References 1867 Hydroprocessing 187
7.1 Catalytic Conversion Processes 187
7.2 Feed Specifications 194
7.3 Feed Boiling Range 196
7.4 Catalyst 196
7.5 Poor Gas Distribution 200
7.6 Poor Mixing of Reactants 200
7.7 The Mechanism of Hydrocracking 200
7.8 Thermodynamics and Kinetics of Hydrocracking 201
7.9 Process Design, Rating and Performance 204
7.10 Increased ¿P 210
7.11 Factors Affecting Reaction Rate 214
7.12 Measurement of Performance 215
7.13 Catalyst-Bed Temperature Profiles 216
7.14 Factors Affecting Hydrocracking Process Operation 217
7.15 Hydrocracking Correlations 217
7.16 Hydrocracker Fractionating Unit 228
7.17 Operating Variables 231
7.18 Hydrotreating Process 234
7.19 Thermodynamics of Hydrotreating 240
7.20 Reaction Kinetics 243
7.21 Naphtha Hydrotreating 245
7.22 Atmospheric Residue Desulfurization 250
7.23 Health, Safety and Environment Considerations 258
References 258
8 Catalytic Cracking 259
8.1 Introduction 259
8.2 Fluidized Bed Catalytic Cracking 262
8.2.1 Process Description 262
8.3 Modes of Fluidization 269
8.4 Cracking Reactions 270
8.5 Thermodynamics of FCC 273
8.6 Process Design Variables 278
8.7 Material and Energy Balances 281
8.8 Heat Recovery 283
8.9 FCC Yield Correlations 284
8.10 Estimating Potential Yields of FCC Feed 286
8.11 Pollution Control 290
8.12 New Technology 292
8.13 Refining/Petrochemical Integration 296
8.14 Metallurgy 296
8.15 Troubleshooting for Fluidized Catalyst Cracking Units 297
8.16 Health, Safety and Environment Considerations 298
8.17 Licensors' Correlations 299
8.18 Simulation and Modeling Strategy 300
References 3049 Catalytic Reforming and Isomerization 305
9.1 Introduction 305
9.2 Catalytic Reforming 306
9.3 Feed Characterization 306
9.4 Catalytic Reforming Processes 308
9.5 Operations of the Reformer Process 312
9.6 Catalytic Reformer Reactors 316
9.7 Material Balance in Reforming 317
9.8 Reactions 320
9.9 Hydrocracking Reactions 322
9.10 Reforming Catalyst 322
9.11 Coke Deposition 324
9.12 Thermodynamics 326
9.13 Kinetic Models 326
9.14 The Reactor Model 326
9.15 Modeling of Naphtha Catalytic Reforming Process 329
9.16 Isomerization 329
9.17 Sulfolane Extraction Process 331
9.18 Aromatic Complex 333
9.19 Hydrodealkylation Process 336
References 33710 Alkylation and Polymerization Processes 339
10.1 Introduction 339
10.2 Chemistry of Alkylation 340
10.3 Catalysts 342
10.4 Process Variables 343
10.5 Alkylation Feedstocks 345
10.6 Alkylation Products 346
10.7 Sulfuric Acid Alkylation Process 346
10.8 HF Alkylation 347
10.9 Kinetics and Thermodynamics of Alkylation 351
10.10 Polymerization 354
10.11 HF and H2SO4 Mitigating Releases 354
10.12 Corrosion Problems 356
10.13 A New Technology of Alkylation Process Using Ionic Liquid 356
10.14 Chevron - Honeywell UOP Ionic liquid Alkylation 357
10.15 Chemical Release and Flash Fire: A Case Study of the Alkylation Unit at the Delaware City Refining Company (DCRC) Involving Equipment Maintenance Incident 358
References 362
11 Hydrogen Production and Purification 365
11.1 Hydrogen Requirements in a Refinery 365
11.2 Process Chemistry 366
11.3 High-Temperature Shift Conversion 368
11.4 Low-Temperature Shift Conversion 368
11.5 Gas Purification 368
11.6 Purification of Hydrogen Product 369
11.7 Hydrogen Distribution System 370
11.8 Off-Gas Hydrogen Recovery 371
11.9 Pressure Swing Adsorption (PSA) Unit 371
11.10 Refinery Hydrogen Management 375
11.11 Hydrogen Pinch Studies 377
References 379
12 Gas Processing and Acid Gas Removal 381
12.1 Introduction 381
12.2 Diesel Hydrodesulfurization (DHDS) 383
12.3 Hydrotreating Reactions 383
12.4 Gas Processing 388
12.5 Sulfur Management 391
12.6 Physical Solvent Gas Processes 401
12.7 Carbonate Process 402
12.8 Solution Batch Process 403
12.9 Process Description of Gas Processing using UniSim® Simulation 405
12.10 Gas Dryer (Dehydration) Design 410
12.11 Kremser-Brown-Sherwood Method-No Heat of Absorption 415
12.12 Absorption: Edmister Method 421
12.13 Gas Treating Troubleshooting 432
12.14 Cause - Loss of Glycol Out of Still Column 434
12.15 The ADIP Process 435
12.16 Sour Water Stripping Process 435
References 438Glossary of Petroleum and Technical Terminology 441
Appendix A Equilibrium K values 533
Appendix B Analytical Techniques 547
Appendix C Physical and Chemical Characteristics of Major Hydrocarbons 557
Appendix D A List of Engineering Process Flow Diagrams and Process Data Sheets 573
Index 623
Chapter 1
Introduction
Petroleum and natural gas have been the essential source of energy production worldwide, greater than nuclear and alternative sources such as solar, wind and geothermal. With globalization, global energy demand will continue to increase for the foreseeable future. Oil and natural gas will continue to supply a majority of the world's energy needs, and the production will be from natural sources of petroleum, coal and natural gas. The U.S. has an estimated 260 billion tons of recoverable coal, equivalent to three or four times as much energy in coal as Saudi Arabia has in oil [1]. This increase requires the exploitation of conventional and unconventional reservoirs of oil and gas in an environmentally friendly manner that requires advances in technology and materials in the form of better catalysts to produce clean fuels.
The National Petroleum Council (NPC) in the U.S. [2] indicates that the total global demand for energy will grow by 50 - 60% by 2030 due to the increase in world population, and the average standards of living in the developing countries. Therefore, oil, gas and coal will continue to be the primary energy sources notwithstanding the discovery of bio-fuels such as bio-ethanol for the twenty-first century. Further, the energy industry will require an increase in the supply of hydrocarbon resources to meet these demands. The volumes of oil and natural gas located in unconventional reservoirs are much larger than the conventional reservoirs, which are currently used for what has been produced. Unconventional oil and gas are generally difficult and expensive to extract, and may present a more negative environmental impact than conventional reserves. Examples of unconventional oil sources are extra heavy oil, oil sands, tight sands, oil shale, etc. Extracting oil and gas from unconventional reservoirs requires developing new technology that enables the industry to produce oil and gas in an environmentally acceptable manner. Carbon dioxide (CO2) sequestration and environmentally friendly processes will form a prominent aspect of developing new resources. Throughout these processes, development of materials of construction for the facilities, especially those that can withstand high-temperature, high-pressure and high-stress conditions will be essential to the entire industry [3].
The recent low oil price (U.S. $55/bbl) in 2015, unlike 2008, is triggered by:
- A weak demand growth, particularly in China and Europe.
- Strong non-OPEC supplied growth, particularly from U.S. tight oil.
- OPEC's behavior as it has maintained production to retain market share.
The global demand for oil in 2000 was 76 million barrels per day (bbls per day), while currently oil production is about 86 million bbls per day (40,000 gallons per second) or 31.4 billion barrels per year. The NPC estimates that the demand for oil will be 103-138 millions bbls per day or 37.6-50.4 billions bbls per year by 2030. Global conventional oil reserves are mainly in the Middle East, and the seven countries with the largest conventional oil reserves account for more than 70% of the world total. Saudi Arabia holds 20% of the conventional reserves [3].
In the early 1990s, Saudi Arabia held 18.9% of the global crude oil/refined product export market. The market share fell to a low 12.4% in 2014, which notably is the same market share when OPEC took a stance and flooded the international oil market with the goal to control its market share as in 1986. The mid-1980s were disappointing and unprofitable for both the upstream and downstream until corrections in supply and demand lifted oil pricing to an agreeable level for producers as Saudi Arabia and OPEC.
Figure 1.1 shows Wood Mackenzie's global demand outlook, and first-quarter and second-quarter 2015 demand levels projected to be lower than that of the fourth-quarter 2014, reflecting seasonality and refinery maintenance. U.S. tight oil is the most responsive supply source that requires drilling a large number of wells, each of which declines rapidly. Low oil prices will impact the growth from this supply source, which will eventually resolve in returning the oil market back into balance. Refining industry margins and crude runs have been supported by the declining oil price during the second half of 2014, as oil product prices have reduced as shown in Figure 1.2.
Figure 1.1 Quarterly global demand outlook 2014 - 2015 (Source: Gelder, Alan, pp 25. Hydrocarbon Processing, February 2015 [4]).
Figure 1.2 Regional gross refining margins, US$/bbl. (Source: Gelder, Alan, Hydrocarbon Processing, pp 25, February 2015 [4]).
Refiners are encountering a dynamic business environment as crude prices are volatile, heavy, high-sulfur and acidic opportunity crudes are increasingly available. Demand for lighter products is increasing, product legislation and emissions standards are tightening and health, safety and environment mandates also have to be met.
The demand for transportation fuels continues to increase, which is driven by the expanding economies of developing nations in Asia-Pacific, the Middle East and Latin America, and global demand for crude oil is forecast to exceed 94 MMbpd in 2015. Presently there are over 640 refineries that are operating globally and the refining industry is struggling with excess capacity. Demand for transportation fuels is shifting toward other middle distillates and diesel. Figure 1.3 shows a map of the world crude oil reserves.
Figure 1.3 World oil reserves. (Source: OPEC Annual Statistical Bulletin, 2012).
Refining Processes and Operations
Crude oil in its natural state has no value to consumers unless it is processed into products that are marketable. Various physical and chemical methods are employed in the refining processes. These methods apply process conditions as temperature, pressure, catalysts, heat and chemical reactions to convert crude oil and other hydrocarbons into petroleum products.
Refining commences with distillation by boiling crude into separate fractions or cuts. All crude oils undergo separation processes through distillation and the capacity of a refinery is expressed in terms of its distillation capacity. Two measures are commonly used: barrels per stream day (bpsd) and barrels per calendar day (bpcd). A barrel per stream day is the maximum number of barrels of input that a distillation facility can process when running at full capacity under optimal crude and product slate conditions with no allowance for downtime. A barrel per calendar day is the amount of input that a distillation facility can process under usual operating conditions, making allowances for the types and grades of products to be manufactured, environmental constraints, scheduled and unscheduled downtime due to maintenance, repairs and shutdown. Table 1.1 shows the world's largest refiners with their intakes of crudes of thousand bbls per calendar day.
Table 1.1 shows the world's largest refiners.
Rank by capacity Company Crude capacity thousand barrels per calendar day 1 Exxon Mobil Corporation (USA) 5,589 2 Royal Dutch / Shell (Netherlands) 4,109 3 Sinopec (China) 3,971 4 BP, plc (United Kingdom) 2,859 5 Saudi Arabian Oil Company (Saudi Arabia) 2,852 6 Valero Energy Company (USA) 2,777 7 Petroleoes de Venezuela. S.A. (Venezuela) 2,678 8 China National Petroleum Company (China) 2,675 9 Chevron Corporation (USA) 2,540 10 Phillips 66 (USA) 2,514 11 Total S.A. (France) 2,304 12 Petroleo Brasilerio S.A. (Brazil) 1,997 13 Marathon Oil Corp (USA) 1,714 14 Petroleos Mexicanos (Mexico) 1,703 15 National Iranian Oil Company (Iran) 1,451 16 JX Nippon Oil & Energy Corp (Japan) 1,423 17 Rosneft (Russia) 1,293 18 OAO Lukoil (Russia) 1,217 19 SK Innovation (South Korea) 1,115 20 Repsol YPF S.A. (Spain) 1,105 21 Kuwait National Petroleum Corporation (Kuwait) 1,085 22 Pertamina (Indonesia) 993 23 Agip Petroli SpA (Italy) 904 24 Flint Hills...