Table Of ContentHandbook of
PETROLEUM
REFINING
CHEMICAL INDUSTRIES
A Series of Reference Books and Textbooks
Founding Editor
HEINZ HEINEMANN
Berkeley, California
Series Editor
JAMES G. SPEIGHT
CD & W, Inc.
Laramie, Wyoming
MOST RECENTLY PUBLISHED
Handbook of Petroleum Refining, James G. Speight
Handbook of Refinery Desulfurization, Nour Shafik El-Gendy and James G. Speight
Petroleum and Gas Field Processing, Second Edition, Hussein K. Abdel-Aal,
Mohamed A. Aggour, and Mohamed A. Fahim
Refining Used Lubricating Oils, James Speight and Douglas I. Exall
The Chemistry and Technology of Petroleum, Fifth Edition, James G. Speight
Transport Phenomena Fundamentals, Third Edition, Joel Plawsky
Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology,
Second Edition, Leslie R. Rudnick
Modeling of Processes and Reactors for Upgrading of Heavy Petroleum,
Jorge Ancheyta
Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology,
Second Edition, Leslie R. Rudnick
Fundamentals of Automatic Process Control, Uttam Ray Chaudhuri and
Utpal Ray Chaudhuri
The Chemistry and Technology of Coal, Third Edition, James G. Speight
Practical Handbook on Biodiesel Production and Properties, Mushtaq Ahmad,
Mir Ajab Khan, Muhammad Zafar, and Shazia Sultana
Introduction to Process Control, Second Edition, Jose A. Romagnoli
and Ahmet Palazoglu
Fundamentals of Petroleum and Petrochemical Engineering, Uttam Ray Chaudhuri
Advances in Fluid Catalytic Cracking: Testing, Characterization, and
Environmental Regulations, edited by Mario L. Occelli
Advances in Fischer-Tropsch Synthesis, Catalysts, and Catalysis,
edited by Burtron H. Davis and Mario L. Occelli
Transport Phenomena Fundamentals, Second Edition, Joel Plawsky
Asphaltenes: Chemical Transformation during Hydroprocessing of Heavy Oils,
Jorge Ancheyta, Fernando Trejo, and Mohan Singh Rana
Handbook of
PETROLEUM
REFINING
JAMES G. SPEIGHT
CRC Press
Taylor & Francis Group
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© 2017 by Taylor & Francis Group, LLC
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Version Date: 20160805
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Library of Congress Cataloging‑in‑Publication Data
Names: Speight, James G., author.
Title: Handbook of petroleum refining / James G. Speight.
Description: Boca Raton : Taylor & Francis, a CRC title, part of the Taylor &
Francis imprint, a member of the Taylor & Francis Group, the academic
division of T&F Informa, plc, [2017] | Series: Chemical industries ; 143 |
Includes bibliographical references and index.
Identifiers: LCCN 2016008773 | ISBN 9781466591608 (alk. paper)
Subjects: LCSH: Petroleum--Refining--Handbooks, manuals, etc.
Classification: LCC TP690 .S743 2017 | DDC 622/.338--dc23
LC record available at https://lccn.loc.gov/2016008773
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
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Contents
Preface............................................................................................................................................xvii
Author .............................................................................................................................................xix
Section i Feedstock: Availability and evaluation
Chapter 1 Crude Oil, Heavy Oil, and Tar Sand Bitumen .............................................................3
1.1 Introduction .......................................................................................................3
1.2 Native Materials ................................................................................................4
1.2.1 Petroleum..............................................................................................4
1.2.1.1 Crude Oil from Tight Formations .......................................10
1.2.1.2 Opportunity Crudes ............................................................11
1.2.1.3 High-Acid Crude Oil ..........................................................12
1.2.1.4 Foamy Oil ...........................................................................13
1.2.2 Heavy Oil ...........................................................................................14
1.2.3 Tar Sand Bitumen ...............................................................................19
1.2.4 Kerogen ..............................................................................................24
1.2.5 Biomass ..............................................................................................25
1.3 Natural Gas ......................................................................................................27
1.3.1 Petroleum-Related Gas .......................................................................28
1.3.2 Gas Hydrates ......................................................................................32
1.3.3 Coalbed Methane ...............................................................................32
1.3.4 Biogenic Gas ......................................................................................33
1.4 Manufactured Materials ..................................................................................33
1.4.1 Residuum ............................................................................................33
1.4.2 Asphalt ...............................................................................................34
1.4.3 Synthetic Crude Oil ............................................................................35
1.4.4 Shale Oil .............................................................................................36
1.5 Derived Materials ............................................................................................36
1.5.1 Asphaltene Constituents .....................................................................37
1.5.2 Nonasphaltene Constituents ...............................................................37
1.6 Resources and Reserves ..................................................................................37
1.6.1 Conventional Crude Oil and Heavy Oil .............................................40
1.6.2 Tar Sand Bitumen ...............................................................................40
1.6.3 Natural Gas ........................................................................................41
References ..................................................................................................................42
Chapter 2 Feedstock Evaluation..................................................................................................45
2.1 Introduction .....................................................................................................45
2.2 Petroleum Assay ..............................................................................................47
2.3 Physical Properties ..........................................................................................52
2.3.1 Acid Number ......................................................................................54
2.3.1.1 Potentiometric Titration ......................................................55
2.3.1.2 Color-Indicating Titration ...................................................55
v
vi Contents
2.3.2 Elemental Analysis .............................................................................56
2.3.3 Density and Specific Gravity .............................................................57
2.3.4 Metal Content .....................................................................................59
2.3.5 Surface and Interfacial Tension ..........................................................60
2.3.6 Viscosity .............................................................................................62
2.4 Thermal Properties ..........................................................................................64
2.4.1 Aniline Point ......................................................................................65
2.4.2 Carbon Residue ..................................................................................65
2.4.3 Critical Properties ..............................................................................67
2.4.4 Enthalpy .............................................................................................69
2.4.5 Heat of Combustion ............................................................................69
2.4.6 Latent Heat .........................................................................................70
2.4.7 Liquefaction and Solidification ..........................................................70
2.4.8 Pressure–Volume–Temperature Relationships ...................................72
2.4.9 Specific Heat ......................................................................................72
2.4.10 Thermal Conductivity ........................................................................73
2.4.11 Volatility .............................................................................................73
2.5 Electrical Properties ........................................................................................76
2.5.1 Conductivity .......................................................................................76
2.5.2 Dielectric Constant .............................................................................77
2.5.3 Dielectric Strength .............................................................................78
2.5.4 Dielectric Loss and Power Factors .....................................................78
2.5.5 Static Electrification ...........................................................................79
2.6 Optical Properties ............................................................................................79
2.6.1 Optical Activity ..................................................................................79
2.6.2 Refractive Index .................................................................................80
2.7 Spectroscopic Properties .................................................................................81
2.7.1 Infrared Spectroscopy ........................................................................82
2.7.2 Mass Spectrometry .............................................................................82
2.7.3 Nuclear Magnetic Resonance Spectroscopy ......................................83
2.8 Chromatographic Properties ...........................................................................83
2.8.1 Adsorption Chromatography ..............................................................83
2.8.2 Gas Chromatography .........................................................................85
2.8.3 Gel Permeation Chromatography .......................................................87
2.8.4 High-Performance Liquid Chromatography ......................................88
2.8.5 Ion-Exchange Chromatography .........................................................89
2.8.6 Simulated Distillation.........................................................................90
2.8.7 Supercritical Fluid Chromatography ..................................................91
2.9 Molecular Weight ............................................................................................91
2.10 Use of the Data ................................................................................................92
References ..................................................................................................................94
Chapter 3 Feedstock Composition ............................................................................................101
3.1 Introduction ...................................................................................................101
3.2 Elemental Composition .................................................................................102
3.3 Chemical Composition ..................................................................................104
3.3.1 Hydrocarbon Constituents ................................................................107
3.3.1.1 Paraffin Hydrocarbons ......................................................108
3.3.1.2 Cycloparaffin Hydrocarbons .............................................109
Contents vii
3.3.1.3 Aromatic Hydrocarbons ...................................................110
3.3.1.4 Unsaturated Hydrocarbons ...............................................113
3.3.2 Nonhydrocarbon Constituents ..........................................................113
3.3.2.1 Sulfur Compounds ............................................................114
3.3.2.2 Nitrogen Compounds ........................................................116
3.3.2.3 Oxygen Compounds .........................................................118
3.3.2.4 Metallic Constituents ........................................................118
3.3.2.5 Porphyrins .........................................................................119
3.4 Chemical Composition by Distillation ..........................................................121
3.4.1 Gases and Naphtha ...........................................................................123
3.4.2 Middle Distillates .............................................................................124
3.4.3 Vacuum Residua ...............................................................................126
3.5 Fractional Composition .................................................................................127
3.5.1 Solvent Methods ...............................................................................128
3.5.2 Adsorption Methods .........................................................................133
3.5.3 Chemical Methods ...........................................................................135
3.6 Use of the Data ..............................................................................................135
References ................................................................................................................139
Chapter 4 Introduction to Refining Processes ..........................................................................143
4.1 Introduction ...................................................................................................143
4.2 Dewatering and Desalting .............................................................................147
4.3 Distillation .....................................................................................................148
4.3.1 Distillation at Atmospheric Pressure................................................149
4.3.2 Distillation under Reduced Pressure ................................................150
4.3.3 Azeotropic and Extractive Distillation .............................................151
4.4 Thermal Processes .........................................................................................152
4.4.1 Thermal Cracking ............................................................................154
4.4.2 Visbreaking ......................................................................................155
4.4.3 Coking ..............................................................................................155
4.4.3.1 Delayed Coking ................................................................157
4.4.3.2 Fluid Coking .....................................................................157
4.5 Catalytic Processes ........................................................................................159
4.5.1 Catalytic Cracking............................................................................159
4.5.2 Catalysts ...........................................................................................160
4.6 Hydroprocesses ..............................................................................................162
4.6.1 Hydrotreating ...................................................................................163
4.6.1.1 Hydrofining .......................................................................163
4.6.2 Hydrocracking ..................................................................................163
4.7 Reforming Processes .....................................................................................165
4.7.1 Thermal Reforming ..........................................................................165
4.7.2 Catalytic Reforming .........................................................................166
4.7.3 Catalysts ...........................................................................................167
4.8 Isomerization Processes ................................................................................167
4.8.1 Processes ..........................................................................................168
4.8.2 Catalysts ...........................................................................................168
4.9 Alkylation Processes .....................................................................................169
4.9.1 Processes ..........................................................................................170
4.9.2 Catalysts ...........................................................................................170
viii Contents
4.10 Polymerization Processes ..............................................................................170
4.10.1 Processes ..........................................................................................171
4.10.2 Catalysts ...........................................................................................171
4.11 Solvent Processes...........................................................................................171
4.11.1 Deasphalting .....................................................................................172
4.11.2 Dewaxing .........................................................................................173
4.12 Petroleum Products ........................................................................................174
4.13 Petrochemicals ...............................................................................................175
4.14 Ancillary Operations .....................................................................................177
References ................................................................................................................178
Chapter 5 Refining Chemistry ..................................................................................................181
5.1 Introduction ...................................................................................................181
5.2 Cracking Chemistry ......................................................................................183
5.2.1 Thermal Cracking ............................................................................183
5.2.1.1 General Chemistry ............................................................183
5.2.1.2 Asphaltene Chemistry ......................................................186
5.2.1.3 Biomass Chemistry ...........................................................188
5.2.2 Catalytic Cracking............................................................................188
5.2.3 Dehydrogenation ..............................................................................190
5.2.4 Dehydrocyclization ...........................................................................193
5.3 Hydrogenation ...............................................................................................193
5.3.1 Hydrotreating ...................................................................................194
5.3.1.1 General Chemistry ............................................................194
5.3.1.2 Asphaltene Chemistry ......................................................194
5.3.1.3 Catalysts ............................................................................196
5.3.2 Hydrocracking ..................................................................................196
5.3.2.1 General Chemistry ............................................................197
5.3.2.2 Asphaltene Chemistry ......................................................198
5.3.2.3 Catalysts ............................................................................198
5.3.3 Solvent Deasphalting ........................................................................199
5.3.3.1 Effects of Temperature and Pressure ................................199
5.3.3.2 Effects of the Solvent-to-Oil Ratio ...................................200
5.3.3.3 Effects of Solvent Types ...................................................200
5.4 Isomerization .................................................................................................201
5.5 Alkylation ......................................................................................................202
5.6 Polymerization ...............................................................................................202
5.7 Process Chemistry .........................................................................................202
5.7.1 Thermal Chemistry ..........................................................................203
5.7.2 Hydroconversion Chemistry .............................................................211
5.7.3 Chemistry in the Refinery ................................................................212
5.7.3.1 Visbreaking .......................................................................212
5.7.3.2 Hydroprocessing ...............................................................215
References ................................................................................................................216
Chapter 6 Refinery Reactors .....................................................................................................221
6.1 Introduction ...................................................................................................221
6.2 Reactor Types ................................................................................................226
6.2.1 Batch Reactors ..................................................................................227
6.2.1.1 Heating and Cooling Systems ...........................................228
Contents ix
6.2.2 Semibatch Reactors ..........................................................................230
6.2.3 Continuous Reactors ........................................................................230
6.2.4 Plug Flow Reactors ...........................................................................232
6.2.5 Flash Reactors ..................................................................................232
6.2.6 Slurry Reactors .................................................................................233
6.3 Bed Types ......................................................................................................234
6.3.1 Packed Beds .....................................................................................234
6.3.2 Plug Flow Reactors ...........................................................................238
6.3.3 Fluidized-Bed Reactors ....................................................................238
6.3.4 Downflow Fixed-Bed Reactors ........................................................240
6.3.5 Upflow Expanded-Bed Reactors ......................................................241
6.3.6 Ebullating Bed Reactors ...................................................................241
6.3.7 Demetallization Reactors .................................................................242
6.4 Process Parameters ........................................................................................243
6.4.1 Partial Pressure ................................................................................244
6.4.2 Space Velocity ..................................................................................244
6.4.3 Temperature ......................................................................................244
6.4.4 Catalyst Life .....................................................................................245
6.4.5 Feedstock ..........................................................................................245
References ................................................................................................................247
Section ii Refining
Chapter 7 Pretreatment and Distillation ...................................................................................251
7.1 Introduction ...................................................................................................251
7.2 Dewatering and Desalting .............................................................................253
7.3 Distillation .....................................................................................................259
7.3.1 Distillation at Atmospheric Pressure................................................264
7.3.2 Distillation at a Reduced Pressure ...................................................268
7.3.3 Distillation Towers ...........................................................................272
7.3.3.1 Tray Towers.......................................................................273
7.3.3.2 Packed Towers ..................................................................275
7.4 Other Distillation Processes ..........................................................................277
7.4.1 Stripping ...........................................................................................277
7.4.2 Rerunning .........................................................................................278
7.4.3 Stabilization ......................................................................................278
7.4.4 Superfractionation ............................................................................281
7.4.5 Azeotropic Distillation .....................................................................281
7.4.6 Extractive Distillation ......................................................................282
7.5 Options for Heavy Feedstocks .......................................................................285
7.5.1 Distillation Operations .....................................................................285
7.5.2 Corrosion ..........................................................................................287
References ................................................................................................................288
Chapter 8 Thermal Cracking Processes ....................................................................................291
8.1 Introduction ...................................................................................................291
8.2 Thermal Cracking .........................................................................................296
8.3 Visbreaking ...................................................................................................299
x Contents
8.4 Coking ...........................................................................................................315
8.4.1 Delayed Coking ................................................................................316
8.4.2 Fluid Coking .....................................................................................321
8.4.3 Flexicoking .......................................................................................329
8.5 Other Processes .............................................................................................330
8.6 Options for Heavy Feedstocks .......................................................................332
8.6.1 Aquaconversion Process ...................................................................332
8.6.2 Asphalt Coking Technology (ASCOT) Process ...............................332
8.6.3 Cherry-P Process ..............................................................................333
8.6.4 Continuous Coking Process .............................................................333
8.6.5 Decarbonizing Process .....................................................................334
8.6.6 ET-II Process ....................................................................................334
8.6.7 Eureka Process .................................................................................335
8.6.8 FTC Process .....................................................................................336
8.6.9 HSC Process .....................................................................................336
8.6.10 Mixed-Phase Cracking Process........................................................336
8.6.11 Selective Cracking Process ..............................................................337
8.6.12 Shell Thermal Cracking Process ......................................................337
8.6.13 Tervahl-T Process .............................................................................338
References ................................................................................................................339
Chapter 9 Catalytic Cracking Processes ...................................................................................341
9.1 Introduction ...................................................................................................341
9.2 Fixed-Bed Processes ......................................................................................349
9.3 Moving-Bed Processes ..................................................................................350
9.4 Fluid-Bed Processes ......................................................................................354
9.5 Coke Formation and Additives ......................................................................361
9.5.1 Coke Formation ................................................................................361
9.5.2 Additives ...........................................................................................363
9.6 Process Variables ...........................................................................................363
9.6.1 Feedstock Quality ............................................................................363
9.6.2 Feedstock Preheating .......................................................................367
9.6.3 Feedstock Pressure ...........................................................................368
9.6.4 Feedstock Conversion .......................................................................368
9.6.5 Reactor Temperature ........................................................................369
9.6.6 Recycle Rate .....................................................................................370
9.6.7 Space Velocity ..................................................................................370
9.6.8 Catalyst Activity ...............................................................................371
9.6.9 Catalyst/Oil Ratio .............................................................................371
9.6.10 Regenerator Temperature .................................................................373
9.6.11 Regenerator Air Rate ........................................................................373
9.6.12 Process Design .................................................................................373
9.6.12.1 Modifications for Existing Units ......................................373
9.6.12.2 Commercial Technology Changes ....................................374
9.6.12.3 New Directions .................................................................376
9.7 Catalysts ........................................................................................................376
9.7.1 Catalyst Types ..................................................................................377
9.7.2 Catalyst Manufacture .......................................................................379
9.7.3 Catalyst Selectivity ...........................................................................380
9.7.4 Catalyst Deactivation .......................................................................381
