Petroleum Refining Volume 1

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Petroleum Refining Volume 1

Petroleum Refining, Crude Oil, Petroleum Products and Process Flowsheets Volume 1

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Refining has the function of transforming crude oil from various origins into a set of refined products in accordance with precise specifications and in quantities corresponding as closely as possible to the market requirements. Crude oils present a wide variety of physical and chemical properties. Among the more important characteristics are the following:

• distillation curve, which leads to a first classification of light crude oils having high distillate yields as opposed to heavy or extra heavy crudes
• sulfur content (crudes having low or high contents)
• chemical composition, this is used only to characterize particular crudes (paraffinic or naphthenic).

As a whole, a given crude is generally used to make products most of which have positive added values. This is particularly the case for motor fuels and specialty products. However, some of the products could have negative added values, as in the case of unavoidable products like heavy fuels and certain petroleum cokes.

The products could be classified as a function of various criteria: physical properties (in particular, volatility), the way they are created (primary distillation or conversion). Nevertheless, the classification most relevant to this discussion is linked to the end product use: LPG, premium gasoline, kerosene and diesel oil, medium and heavy fuels, specialty products like solvents, lubricants, and asphalts. Indeed, the product specifications are generally related to the end use. Traditionally, they have to do with specific properties: octane number for premium gasoline, cetane number for diesel oil as well as overall physical properties such as density, distillation curves and viscosity.

Chapter 1 Composition of Crude Oils and Petroleum Products
1.1 Pure Components 1
1.1.1 Hydrocarbons•— 3
1.1.2 Non-Hydrocarbon Compounds 8
1.2 Compounds whose Chemistry is Incompletely Defined 13
1.2.1 Asphaltenes 13
1.2.2 Resins 15

Chapter 2 Fractionation and Elemental Analysis of Crude Oils and Petroleum Cuts
2.1 Preparatory and Analytical Fractionations 17
2.1.1 Distillation 17
2.1.2 Other Separations 24
2.2 Elemental Analysis 27
2.2.1 Some Definitions 28
2.2.2 Sampling 28
2.2.3 Analysis of Carbon, Hydrogen and Nitrogen 28
2.2.4 Oxygen Analysis • 30
2.2.5 Sulfur Analysis 31
2.2.6 Analysis of Metals in Petroleum Cuts 34
XIV Contents

Chapter 3 Characterization of Crude Oils and Petroleum Fractions
3. 1 Characterization of Crude Oils According to Dominant Characteristics Based on Overall Physical Properties 39
3.1.1 Characterization of Crude Oils Using Specific Gravities of a Light Fraction and a Heavy Fraction 40
3.1.2 Characterization Factor, Kyop or Watson Factor Kw 40
3.1.3 Characterization of a Petroleum Cut by Refractive Index, Density, and Molecular Weight (ndM method) 42
3.2 Characterization of Crude Oils and Petroleum Fractions Based on Structural Analysis . 44
3.2.1 Analysis by Hydrocarbon Family 44
3.2.2 Characterization of a Petroleum Fraction by Carbon Atom Distribution 56
3.3 Characterization of Petroleum Fractions by Chromatographic Techniques 70
3.3.1 Analysis of Permanent Gases and Noncondensable Hydrocarbons by Gas Phase Chromatography 70
3.3.2 Analysis of Hydrocarbons Contained in a Gasoline by Gas Phase Chromatography 73
3.3.3 Specific Analysis for Normal Paraffins by Gas Phase Chromatography 73
3.3.4 Specific Detectors in Gas Phase Chromatography 76
3.3.5 Analysis by Fluorescent Indicator in Liquid Chromatography 79
3.3.6 Analysis of Aromatics in Diesel Motor Fuels by Liquid Chromatography 81
3.3.7 SARA Analysis of Heavy Fractions by Preparative Liquid Chromatography 81
3.4 Characterization of Petroleum Fractions Based on Chemical Reactions 83
3.4.1 Bromine Number 83
3.4.2 Maleic Anhydride Value 84

Chapter 4 Methods for the Calculation of Hydrocarbon Physical Properties
4.1 Characterization Required for Calculating Physical Properties 86
4.1.1 Characteristics of Pure Hydrocarbons 86
4.1.2 Characterization of Petroleum Fractions 93
4. 1 .3 Characterization of Mixtures of Pure Hydrocarbons and Petroleum Fractions (Petroleum Cuts) 98
4.2 Basic Calculations of Physical Properties 106
4.2.1 Properties of Pure Hydrocarbons and Petroleum Fractions 108
4.2.2 Properties of Mixtures 109
4.2.3 Principle of Corresponding States 110
4.3 Properties of Liquids 114
4.3.1 Thermodynamic Properties of Liquids 114
4.3.2 Thermophysical Properties of Liquids 126
4.4 Properties of Gases 137
4.4.1 Thermodynamic Properties of Gases 137
4.4.2 Thermophysical Properties of Gases 142
4.5 Estimation of Properties Related to Phase Changes 147
4.5.1 Phase Equilibria for a Pure Hydrocarbon 148
4.5.2 Phase Equilibria for Mixtures 150
4.5.3 Vapor-Liquid Equilibria 152
4.5.4 Estimation of the Properties Used in Determining the Liquid-Liquid Equilibria 168
4.5.5 Estimation of Properties Needed to Determine Liquid-Solid Equilibria 171

Chapter 5 Characteristics of Petroleum Products for Energy Use (Motor Fuels - Heating Fuels)
5.1 Properties Related to the Optimization of Combustion 178
5.1.1 Fundamentals of Thermochemistry 179
5.1.2 Gasoline Combustion and Corresponding Quality Criteria 187
5.1.3 Diesel Fuel Characteristics Imposed by its Combustion Behavior 212
5.1.4 Combustion of Jet Fuels and Corresponding Quality Criteria 225
5.1.5 Characteristics of Special Motor Fuels 230
5.1.6 Home and Industrial Heating Fuels 232
5.1.7 Properties of Heavy Fuels 235
5.2 Properties Related to Storage and Distribution of Petroleum Products 242
5.2.1 Problems Related to the Storage and Distribution of Gasoline 242
5.2.2 Precautions to Observe for Diesel Fuel Use 246
5.2.3 Problems Related to Storage and Distribution of Jet Fuel 250
5.2.4 Problems Related to Storage of Heavy Fuels 252
5.3 Motor Fuels, Heating Fuels and Environmental Protection 252
5.3.1 Justification for Deep Desulfurization 252
5.3.2 Influence of the Chemical Composition of Motor Fuels and Heating Oils on the Environment 258
XVI CowTEwre

Chapter 6 Characteristics of Non-Fuel Petroleum Products
6.1 Characteristics of Petroleum Solvents 271
6.1.1 Nomenclature and Applications 272
6.1.2 Desired Properties of Petroleum Solvents 273
6.2 Characteristics of Naphthas 275
6.3 Characteristics of Lubricants, Industrial Oils and Related Products 275
6.3.1 Nomenclature and Applications 275
6.3.2 Properties Desired in Lubricants, Industrial Oils and Related Products 281
6.4 Characteristics of Waxes and Paraffins 285
6.4.1 Desired Properties of Waxes and Paraffins 285
6.5 Characteristics of Asphalts (Bitumen) 286
6.5.1 Classification of Bitumen 287
6.5.2 Bitumen Manufacture 288
6.5.3 Bitumen Applications 288
6.5.4 Desired Bitumen Properties 289
6.6 Other Products 290
6.6.1 White Oils 290
6.6.2 Aromatic Extracts 291
6.6.3 Coke 292

Chapter 7 Standards and Specifications of Petroleum Products
7;1 Definitions of the Terms Specification and Standard 293
7.2 Organizations for Standardization 294
7.2.1 Recognized Professional Organizations 294
7.2.2 Official Standards Organizations 295
7.3 Evolution of the Standards and Specifications 296
7.4 Specifications for Petroleum Products in France 297

Chapter S Evaluation of Crude Oils
8.1 Overall Physical and Chemical Properties of Crude Oils Related to Transport, Storage and Price 315
8.1.1 Specific Gravity of Crude Oils 315
8.1.2 Crude Oil Pour Point 317
8.1.3 Viscosity of Crude Oils 318
8.1.4 Vapor Pressure and Flash Point of Crude Oils 319
8.1.5 Sulfur Content of Crude Oils 320
8.1.6 Nitrogen Content of Crude Oils 326
8.1.7 Water, Sediment, and Salt Contents in Crude Oils 326
8.2 TBP Crude Oil Distillation - Analysis of Fractions 331
8.3 Graphical Representation of Analyses and Utilization of the Results 332
8.3.1 Graphical Representation 332
8.3.2 Using the Curves 335

Chapter 9 Additives for Motor Fuels and Lubricants
9.1 Additives for Gasolines 346
9.1.1 Detergent Additives 346
9.1.2 Additives for Improving the Octane Number 349
9.1.3 Biocide Additives 351
9.1.4 Antistatic Additives 351
9.2 Additives for Diesel Fuels 352
9.2.1 Additives for Improving the Cetane Number of Diesel Fuels 352
9.2.2 Detergent Additives for Diesel Fuels 352
9.2.3 Additives for Improving Combustion and for Reducing Smoke and Soot Emissions 353
9.2.4 Additives for Improving the Cold Behavior of Diesel Fuel .. 353
9.2.5 Conclusion 354
9.3 Additives for Lubricants 354
9.3.1 Additives Modifying the Rheological Properties of Lubricating Oils 354
9.3.2 Pour Point Depressants 357
9.3.3 Antioxidant Additives for Lubricants 358
9.3.4 Dispersant and Detergent Additives for Lubricants 358
9.3.5 Extreme-Pressure and Anti-Wear Additives 362
9.3.6 Conclusion 363

Chapter 10 Introduction to Refining
10.1 Historical Survey of Refining 365
10.2 Separation Processes 367
10.2.1 Primary Distillation (Atmospheric Pressure) of Crude Oil ., 367
10.2.2 Secondary Distillation or Vacuum Distillation 367
10.2.3 Processing Vacuum Residue by Solvent Extraction (Deasphalting) 368
10.2.4 Other Separation Processes 370
10.3 Conversion Processes 370
10.3.1 Processes for the Improvement of Properties 371
10.3.2 Conversion Processes 378
10.3.3 Finishing Processes 402
10.3.4 Environmental Protection Processes 404
10.4 The Evolving Refinery Flowscheme 406
10.4.1 The Refinery from 1950 to 1970 406
10.4.2 The Refining Flow Diagram of the 1980s 408
10.4.3 The Refining Flowsheet of the 1990s 408
10.4.4 The Refining Configuration Beyond the Year 2000 411

Appendix 1 Principal Characteristics. of Pure Components 415

Appendix 2 Principal Standard Test Methods for Petroleum Products 445
References 453
Index 461