6th Edition

Petroleum Refining Technology, Economics, and Markets, Sixth Edition

    722 Pages 12 Color & 286 B/W Illustrations
    by CRC Press

    722 Pages 12 Color & 286 B/W Illustrations
    by CRC Press

    For four decades, Petroleum Refining has guided thousands of readers toward a reliable understanding of the field, and through the years has become the standard text in many schools and universities around the world offering petroleum refining classes, for self-study, training, and as a reference for industry professionals.

    The sixth edition of this perennial bestseller continues in the tradition set by Jim Gary as the most modern and authoritative guide in the field. Updated and expanded to reflect new technologies, methods, and topics, the book includes new discussion on the business and economics of refining, cost estimation and complexity, crude origins and properties, fuel specifications, and updates on technology, process units, and catalysts.

    The first half of the book is written for a general audience to introduce the primary economic and market characteristics of the industry and to describe the inputs and outputs of refining. Most of this material is new to this edition and can be read independently or in parallel with the rest of the text. In the second half of the book, a technical review of the main process units of a refinery is provided, beginning with distillation and covering each of the primary conversion and treatment processes. Much of this material was reorganized, updated, and rewritten with greater emphasis on reaction chemistry and the role of catalysis in applications.

    Petroleum Refining: Technology, Economics, and Markets is a book written for users, the practitioners of refining, and all those who want to learn more about the field.

    Part 1. Markets and Economics

    Section 1: Industry Structure and Characteristics

    1. Performance

    1.1 Refinery Supply Chains

    1.1.1 Input-Output Model

    1.1.2 Infrastructure

    1.1.3 Location

    1.1.4 Commercial Requirements

    1.2 Performance

    1.3 Refinery Economics

    1.4 Refining Yields

    1.5 Refining Margins

    1.5.1 Gross Margin

    1.5.2 Net Margin and Netback

    1.5.3 Application

    1.6 Margin Comparisons

    1.6.1 Sweet vs. Sour Crude

    1.6.2 Cracker vs. Coker Refinery

    1.7 Factors That Impact Margins

    1.8 Crack Spreads

    1.9 Market Data

    References

    2. Products

    2.1 Overview

    2.2 Petroleum Gases

    2.2.1 Methane

    2.2.2 Ethane

    2.2.3 Propane

    2.2.4 Butane

    2.2.5 Natural Gas Liquids

    2.3 Light Distillates

    2.3.1 Naphthas

    2.3.2 Gasolines

    2.4 Middle Distillates

    2.4.1 Jet Fuel

    2.4.2 Kerosene

    2.4.3 Automotive Diesel

    2.4.4 Marine Diesel

    2.4.5 Light Fuel Oil

    2.5 Heavy Fuel Oils

    2.6 Specialty Products

    2.6.1 Base Oils and Lubricants

    2.6.2 Engine Oils

    2.6.3 Greases

    2.6.4 Waxes

    2.6.5 Bitumen

    2.6.6 Petroleum Coke

    2.6.7 Carbon Black

    References

    3. Processes

    3.1 Overview

    3.2 Separation

    3.2.1 Perfect Batch Distillation

    3.2.2 Distillation Curves

    3.2.3 Fractions

    3.2.4 Atmospheric Distillation

    3.2.5 Vacuum Distillation

    3.3 Conversion

    3.3.1 Thermal Cracking

    3.3.2 Catalytic Cracking

    3.3.3 Hydrocracking

    3.3.4 Coking

    3.4 Finishing

    3.4.1 Hydrotreating

    3.4.2 Catalytic Reforming

    3.4.3 Alkylation

    3.4.4 Isomerization

    References

    4. Prices

    4.1 Introduction

    4.2 Price Formation

    4.3 Global Oil and Product Markets

    4.4 Price Characteristics

    4.4.1 Prices are Volatile

    4.4.2 Prices are Unpredictable

    4.4.3 Business Cycle Impacts are Periodic

    4.4.4 Price Shocks

    4.4.5 Market Factors Dominate Price Signals

    4.4.6 Private Factors are Secondary in Price Formation

    4.5 Supply and Demand

    4.5.1 Supply Curves

    4.5.2 Demand Curves

    4.5.3 Equilibrium

    4.6 Market Factors

    4.6.1 Demand

    4.6.2 Supply

    4.6.3 Production Cost

    4.6.4 OPEC

    4.6.5 Spare Production Capacity

    4.6.6 Supply Disruptions

    4.6.7 Technology Impacts

    4.7 Private Factors

    4.7.1 Quality

    4.7.2 Yield

    4.8 World Production circa 2017

    4.9 Refined Product Prices

    References

    5. Potpourri

    5.1 Business Model

    5.1.1 Required Spending

    5.1.2 Discretionary Spending

    5.1.3 Capital Investments

    5.2 Company Classification

    5.2.1 Firm Type

    5.2.2 Ownership

    5.2.3 Level of Integration

    5.2.4 Business Objectives

    5.3. U.S. and World Capacity Trends

    5.3.1 Distillation

    5.3.2 Coking

    5.3.3 Catalytic Cracking

    5.3.4 Hydrocracking

    5.3.5 Hydrotreating

    5.3.6 Reforming, Alkylation, Isomerization

    5.3.7 Aromatics and Lubricants

    5.3.8 Hydrogen

    5.3.9 Sulfur

    5.3.10 Asphalt

    5.4. U.S. Capacity Correlations

    5.5 Market Valuation

    5.6 Capital Investment

    References

    Section 2: Cost Estimation and Complexity

    6. Cost Estimation

    6.1 Construction Cost Factors

    6.1.1 ISBL

    6.1.2 USGC Reference

    6.1.3 Project Type

    6.1.4 Unit Addition vs. Grassroots Refinery

    6.1.5 Process Technology

    6.1.6 Process Severity

    6.1.7 Unit Requirements

    6.1.8 Contract Type

    6.1.9 Actual vs. Estimated Cost

    6.1.10 Time

    6.1.11 Location

    6.2 Unit Cost

    6.2.1 Source Data

    6.2.2 Sample Size

    6.2.3 Normalization

    6.3 Cost Functions

    6.3.1 Specification

    6.3.2 Dependent Variable

    6.3.3 Parameter Estimation

    6.3.4 Data Processing

    6.3.5 Data Exclusion

    6.3.6 Cost Envelopes

    6.4 USGC Grassroots Construction Cost

    6.5 Operating Cost Factors

    6.5.1 Common vs. Unique Factors

    6.5.2 Utility Prices

    6.5.3 Capacity, Complexity, Age

    6.5.4 Time

    6.5.5 Location

    6.5.6 Exceptional Events

    6.6 Operating Expenses

    6.6.1 Data Sources

    6.6.2 Consolidation Levels

    6.7 U.S. Operating Cost Statistics, 2010-2014

    References

    7. Refinery Complexity

    7.1 Ideal Refinery

    7.2 Nelson Complexity Index

    7.2.1 Motivation

    7.2.2 Complexity Factor

    7.2.3 Refinery Complexity

    7.3 Complexity Factors

    7.3.1 Definition

    7.3.2 Measurement

    7.3.3 Complexity Cross Factor

    7.3.4 Uncertainty

    7.3.5 Traditional Approach

    7.4 Refinery Complexity

    7.5 U.S. and World Statistics circa 2018

    7.5.1 Regional Capacity

    7.5.2 U.S. Refining Complexity

    7.5.3 Largest World Refineries

    7.5.4 Conversion Capacity

    7.5.5 FCC-Equivalent Capacity

    7.6 Complexity Equation

    7.7 Cost Estimation

    7.8 Complexity Factor at Reference Capacity

    7.8.1 Specification

    7.8.2 U.S. CFRC Statistics

    References

    8. Classification

    8.1 Refinery Categories

    8.2 Very Simple Refinery

    8.3 Simple Refinery

    8.4 Complex Refinery

    8.5 Krotz Springs, Louisiana

    8.6 St. Paul Park, Minnesota

    9. Complexity Applications

    9.1 Introduction

    9.2 Complexity Functional

    9.2.1 Reference Capacity Approach Extension

    9.2.2 Factor Functional Average

    9.2.3 Evaluation

    9.2.4 Closed-Form Expressions

    9.2.5 Comparison

    9.2.6 U.S. Refinery Complexity

    9.3 Complexity Moments

    9.4 Spatial Complexity

    9.5 Replacement Cost

    9.6 Sales Price Models

    9.6.1 Asset Transactions

    9.6.2 Formulation

    9.6.3 Constraints

    9.7 Complexity Barrels

    9.8 Inverse Problem

    9.8.1 Three Refinery Example

    9.8.2 Matrix Formulation

    References

    10. Modern Refineries

    10.1 Hydrocracker

    10.2 Lubes

    10.3 Integrated/Petrochemical

    Section 3: Crude Oil and Properties

    11. Origin and Composition

    11.1 Geologic Time

    11.2 Generation, Migration and Accumulation

    11.2.1 Source Rock

    11.2.2 Generation

    11.2.3 Migration

    11.2.4 Accumulation

    11.2.5 Sedimentary Basins

    11.3 The Hydrocarbon Source

    11.3.1 Origin

    11.3.2 Kerogen Type

    11.3.3 Oil Window

    11.3.4 Transformation Sequence

    11.4 Molecular Composition

    11.4.1 Naming Organic Chemicals

    11.4.2 Early Classifications

    11.4.3 Hydrocarbons

    11.4.4 Paraffin (Alkane) Series

    11.4.5 Naphthene (Cycloparaffin) Series

    11.4.6 Aromatic (Benzene) Series

    11.5 Crude Oil Classification

    11.5.1 Component Groups

    11.5.2 Ternary Diagram

    11.5.3 Tissot-Welte Classification

    11.5.4 Crude Oil Classes

    11.5.6 Marine vs. Nonmarine Organic Matter

    11.5.7 High Sulfur vs. Low Sulfur Oils

    11.6 Alteration and Thermal Maturity Pathways

    11.6.1 Thermal Alteration

    11.6.2 Deasphalting

    11.6.3 Biodegradation

    11.6.4 Water Washing

    Reference

    12. Crude Quality

    12.1 Indicators

    12.1.1 Color

    12.1.2 Density

    12.1.3 Heteroatoms

    12.1.4 Chemical Structure

    12.1.5 Viscosity

    12.2 Classification

    12.3 Blends of Crude Oils

    12.3.1 Additive Properties

    12.3.2 Nonadditive Properties

    References

    13. Distillation Profile

    13.1 Distillation Curves

    13.2 Laboratory Methods

    13.2.1 Standards

    13.2.2 ASTM D86

    13.2.3 ASTM D1160

    13.2.4 ASTM D2892

    13.2.5 ASTM D2887

    13.2.6 ASTM D6352, D7169

    13.3 Hempel Method

    13.3.1 Procedure

    13.3.2 40 mmHg Pressure Correction

    13.3.3 Temperatures Beyond 790°F

    13.3.4 Gravity Midpercent

    13.3.5 Heavy Hydrocarbons

    13.4 Distillation Profile Summary

    13.5 Hasting Field, Texas

    13.6 North Slope Crude, Alaska

    References

    14. Crude Properties

    14.1 Bayon Choctaw and West Hackberry Blends

    14.2 Crude Oil Assay

    14.3 Chemical Properties

    14.3.1 Elemental Analysis

    14.2.2 PNA Composition

    14.3.3 Carbon Residue

    14.4 Composition

    14.4.1 Carbon Hydrogen Ratio

    14.4.2 Sulfur

    14.4.3 Nitrogen

    14.4.4 Metals

    14.4.5 Asphaltenes

    14.4.6 Resins

    14.4.7 Waxes

    14.4.8 Salt Content

    14.4.9 Acid Number

    14.5 Physical Properties

    14.5.1 Molecular Weight

    14.5.2 API Gravity

    14.5.3 UOP Characterization Factor

    14.5.4 Viscosity

    14.5.5 Pour Point

    14.5.6 Reid Vapor Pressure

    References

    15. Fraction Characterization

    15.1 Correlation Relations

    15.2 Carbon Hydrogen Weight Ratio

    15.3 Carbon Residue

    15.4 Asphaltene Content

    15.5 Molecular Weight

    15.6 Aniline Point

    15.7 Smoke Point

    15.8 Viscosity

    15.9 Refractive Index

    15.10 Cloud Point

    15.11 Pour Point

    15.12 Freezing Point

    15.13 Cetane Index

    15.14 Molecular Type Composition

    References

    Section 4: Fuel Specifications

    16. Standards, Specifications and Fuel Quality

    16.1 Types of Specifications

    16.2 Consensus Specifications Definitions

    16.3 Test Methods

    16.4 Transportation Fuel Specifications

    16.4.1 Gasoline – ASTM D4814

    16.4.2 Jet Fuel – ASTM D1653

    16.4.3 Diesel – ASTM D975

    16.4.4 European Automotive Fuels

    16.5 Mandatory and Suggested Specifications

    16.6 Enforcement

    16.7 Fuel Quality

    16.8 Properties Not in Specifications

    References

    17. Gasoline

    17.1 Introduction

    17.2 Octane Number

    17.3 Volatility

    17.3.1 Vapor Pressure

    17.3.2 Distillation Profile

    17.3.3 Vapor-Liquid Ratio

    17.3.4 Vapor Lock Index

    17.3.5 Drivability Index

    17.3.6 Volatility Specifications and Schedules

    17.4 Composition

    17.5 Corrosion

    17.6 Storage and Stability

    17.7 Energy Content

    17.7.1 Heating Value

    17.7.2 Power

    17.7.3 Fuel Economy

    17.8 Additives and Blending Components

    17.9 Fuel Ethanol for Blending

    17.9.1 Purity

    17.9.2 Water, Methanol, Chloride Content

    17.9.3 Acidity

    17.9.4 Sulfur Content

    17.9.5 Denaturants

    17.9.6 Workmanship

    17.10 Aviation Gasoline

    References

    18. Jet Fuels

    18.1 Introduction

    18.2 Specifications

    18.3 Fluidity

    18.4 Volatility

    18.5 Stability

    18.6 Heat Content

    18.7 Combustion Characteristics

    18.8 Composition

    18.9 Lubricity

    18.10 Corrosion

    18.11 Contaminants

    18.12 Additives

    References

    19. Diesel Fuel

    19.1 Introduction

    19.2 Specification

    19.3 Cetane Number

    19.4 Distillation

    19.5 Flash Point

    19.6 Lubricity

    19.7 Ash Content

    19.8 Carbon Residue

    19.9 Low Temperature Operability

    19.10 Stability

    19.11 Blendstocks

    19.12 Biodiesel

    19.13 Other Middle Distillate Products

    References

    20. Product Blending

    20.1 Introduction

    20.2 Gasoline Blendstocks

    20.3 Reid Vapor Pressure

    20.3.1 Theoretical Method

    20.3.2 Blending Indices

    20.4 Octane Blending

    20.5 Blending for Other Properties

    20.6 Gasoline Blending Case Study

    20.7 Ethanol Blending

    20.8 Diesel and Jet Fuel Blendstocks

    References

    Part 2 – Technology

    Section 5: Separation Processes

    21. Crude Oil Desalting

    21.1 Introduction

    21.2 Desalting Technology

    21.2.1 General Description

    21.2.2 Tight Emulsions and Metal Containing Organic Compounds

    References

    22. Crude Oil Distillation

    2.1 Introduction

    22.2 Atmospheric Distillation

    22.2.1 General Description

    22.2.2 Front-End Design Configurations

    22.2.3 Light Naphtha Stabilizer Column

    22.3 Vacuum Distillation

    References

    23. Solvent Deasphalting

    23.1 Introduction

    23.2 Solvent Deasphalting Technology

    23.2.1 General Description

    23.2.2 Bitumen Froth Treatment

    23.3 Deasphalting

    23.3.1 Oil Solubility

    23.3.2 Asphaltenes

    References

    Section 6: Residue Conversion Processes

    24. Visbreaking

    24.1 Introduction

    24.2 Visbreaking Technology

    24.2.1 Feed Material

    24.2.2 General Description

    24.2.3 Hydrovisbreaking and Hydrogen Donor Visbreaking

    24.3 Thermal Cracking

    24.3.1 Reaction Chemistry

    24.3.2 Conversion

    24.3.3 Equivalent Residence Time

    24.4 Visbreaker Operation

    24.4.1 Operating Parameters

    24.4.2 Fuel Properties

    24.4.3 Feed Pretreatment

    References

    25. Coking

    25.1 Introduction

    25.2 Coking Technology

    25.2.1 Feed Material

    25.2.2 Delayed Coking

    25.2.3 Fluid Coking

    25.3 Thermal Carbonization

    25.3.1 Reaction Chemistry and Phase Separation

    25.3.2 Role of Solids

    25.4 Delayed Coker Operation

    25.4.1 Operating Parameters

    25.4.2 Coke Properties

    25.4.3 Fuel Properties

    25.4.4 Yield Estimation

    25.5 Fluid Coker Operation

    25.5.1 Operating Parameters

    25.5.2 Fuel Properties

    25.5.3 Yield Estimates

    References

    26. Residue Hydroconversion

    26.1 Introduction

    26.2 Residue Hydroconversion Technology

    26.2.1 Feed Material

    26.2.2 Reactor Types

    26.2.3 Fixed Bed Residue Hydroconversion

    26.2.4 Moving Bed Residue Hydroconversion

    26.2.5 Ebullated Bed Residue Hydroconversion

    26.5.6 Slurry Bed Residue Hydroconversion

    26.3 Thermal Conversion Combined with Catalytic Hydrotreating

    26.3.1 Reaction Chemistry

    26.3.2 Sediment Formation

    26.3.3 Residue Hydroconversion Catalysts

    26.4 Residue Hydroconversion Operation

    26.4.1 Operating Parameters

    26.4.2 Product Yields

    References

    27. Fluid Catalytic Cracking

    27.1 Introduction

    27.2 Fluid Catalytic Cracking Technology

    27.2.1 Feed Material

    27.2.2 General Description

    27.2.3 Residue Fluid Catalytic Cracking

    27.2.4 FCC for Petrochemicals Production

    27.3 Catalytic Cracking

    27.3.1 Reaction Chemistry

    27.3.2 Conversion

    27.3.3 FCC Catalysts

    27.3.4 Catalyst Deactivation and Equilibrium Catalyst

    27.3.5 Catalyst Additives

    27.4 Fluid Catalytic Cracking Operation

    27.4.1 Operating Parameters

    27.4.2 Pressure Balance

    27.4.3 Heat Balance

    27.4.4 Fuel Properties

    27.4.5 Feed Pretreating

    27.4.6 Yield Estimation

    References

    28. Hydrocracking

    28.1 Introduction

    28.2 Hydrocracking Technology

    28.2.1 Feed Material

    28.2.2 General Description

    28.2.3 Hydroisomerization to Produce Lubricant Base Oil

    28.2.4 Hydrodewaxing

    28.4.5 Mild Hydrocracking

    28.3 Catalytic Hydrocracking

    28.3.1 Reaction Chemistry

    28.3.2 Conversion

    28.3.3 Hydrocracking Catalysts

    28.3.4 Competitive Adsorption

    28.4 Hydrocracker Operation

    28.4.1 Operating Parameters

    28.4.2 Fuel Properties

    28.4.3 Yield Estimates

    References

    Section 7: Distillate, Naphtha, and Gas Conversion Processes

    29. Hydrotreating

    29.1 Introduction

    29.2 Hydrotreating Technology

    29.2.1 Feed Material

    29.2.2 General Description

    29.3 Catalytic Hydrotreating

    29.3.1 Reaction Chemistry

    29.3.2 Reaction Thermodynamics

    29.3.3 Conversion

    29.3.4 Hydrotreating Catalysts

    29.4 Hydrotreater Operation

    References

    30. Butane and Naphtha Hydroisomerization

    30.1 Introduction

    30.2 C4-C6 Hydroisomerization Technology

    30.2.1 Feed Material

    30.2.2 General Description

    30.2.3 Process Configurations with Recycle

    30.3 Catalytic Hydroisomerization

    30.3.1 Reaction Chemistry

    30.3.2 Reaction Thermodynamics

    30.3.3 Hydroisomerization Catalysts

    30.4 C4-C6 Hydroisomerization Operation

    30.4.1 Operating Parameters

    30.4.2 Fuel Properties

    References

    31. Catalytic Naphtha Reforming

    31.1 Introduction

    31.2 Naphtha Reforming Technology

    31.2.1 Feed Material

    31.2.2 General Description

    31.2.3 Catalyst Regeneration Configurations

    31.2.4 Catalyst Regeneration

    31.2.5 Aromatization for Petrochemical Production

    31.3 Catalytic Naphtha Reforming

    31.3.1 Reaction Chemistry

    31.3.2 Conventional Reforming Catalysts

    31.4 Catalytic Naphtha Reforming Operation

    31.4.1 Operating Conditions

    31.4.2 Fuel Properties

    31.4.3 Yield Estimation

    References

    32. Aliphatic Alkylation

    32.1 Introduction

    32.2 Aliphatic Alkylation Technology

    32.2.1 Feed Material

    32.2.2 HF Catalyzed Aliphatic Alkylation

    32.2.3 H2SO4 Catalyzed Aliphatic Alkylation

    32.2.4 Comparison of HF and H2SO4 Catalyzed Processes

    32.3 Reaction Chemistry

    32.3.1 Liquid Acid Catalysts

    32.3.2 Solid Acid Catalysts

    32.4 Aliphatic Alkylation Operation

    32.4.1 Operating Parameters

    32.4.2 Fuel Properties

    References

    33. Olefin Oligomerization

    33.1 Introduction

    33.2 Olefin Oligomerization Technology

    33.2.1 Feed Material

    33.2.2 Fixed Bed Olefin Oligomerization

    33.2.3 Liquid Phase Olefin Oligomerization

    33.2.4 Catalyst Selection

    33.2.5 Refinery Benzene Reduction

    33.3 Reaction Chemistry

    33.3.1 Acid Catalysts

    33.3.2 Organometallic Catalysts

    33.4 Oligomerization Operation

    33.4.1 Operating Parameters

    33.4.2 Fuel Properties

    References

    34. Etherification

    34.1 Introduction

    34.2 Etherification Technology

    34.2.1 Feed Material

    34.2.2 General Description

    34.3 Etherification

    34.3.1 Reaction Chemistry

    34.3.2 Reaction Thermodynamics

    34.3.3 Etherification Catalysts

    34.4 Etherification Operation

    34.4.1 Operating Parameters

    34.4.2 Volumetric Yield

    34.4.3 Fuel Properties of Alcohols and Ethers

    References

    Section 8: Lubricants and Supporting Technologies

    35. Lubricant Base Oils

    35.1 Introduction

    35.2 Lubricant Base Oil Production Technology

    35.2.1 Feed Material

    35.2.2 Technology Selection

    35.2.3 Propane Deasphalting

    35.2.4 Solvent Extraction

    35.2.5 Solvent Dewaxing

    35.2.6 Clay Treating

    References

    36. Supporting Technologies

    36.1 Hydrogen Production and Purification

    36.2 Light Hydrocarbon Gas Processing

    36.3 Acid Gas Removal

    36.4 Sulfur Recovery From Acid Gas

    36.4.1 Claus Process

    36.4.2 Claus Tail Gas Treatment

    References

    Appendix A. Definitions

    Appendix B. Chapter Discussion

    Appendix C. Chapter Problems

    Biography

    Mark J. Kaiser, Arno de Klerk, James H. Gary, Glenn E. Handwerk