Petroleum Refining

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

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