Petroleum

Refining
Technology and
Economics
Fourth Edition

James H. Gary
Colorado School of Mines
Golden, Colorado

Glenn E. Handwerk
Consulting Chemical Engineer
Golden, Colorado

Marcel Dekker, Inc.

TM

Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved.

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Preface

Today refiners are facing investments of billions of dollars in equipment to meet

environmental requirements frequently set by political stipulation with little regard to true economic and environmental impacts. Guidelines set up by laws
and regulations are changed frequently. Since the design and building of new
processing units entail several years of lead time, refiners are reluctant to commit
millions or billions of dollars to constructing equipment that may no longer meet
requirements when the units come on stream. For the short-term period much
effort is being devoted to the development of reformulated fuels that have a minimal impact on degradation of the environment. We say short-term because
laws have already been passed stipulating that within the next two decades hydrocarbon fuel will not be acceptable and only totally nonpolluting fuels will be
acceptable. At the present time the only nonpolluting fuels specified are solar
and electric energy and hydrogen. This allows only a short time for the petroleum
industry to recover the large investment required to meet the present legal requirements. It is apparent that the survivors of this period will be those companies
utilizing the experience and skill of their engineers and scientists to the highest
possible level of efficiency.
In writing this edition, we have taken the new environmental aspects of
the industry into account, as well as the use of heavier crude oils and crude oils
with higher sulfur and metal content. All these criteria affect the processing options and the processing equipment required in a modern refinery.
The basic aspects of current petroleum-refining technology and economics
are presented in a systematic manner suitable for ready reference by technical
managers, practicing engineers, university faculty members, and graduate or senior students in chemical engineering. In addition, the environmental aspects of
refinery fuels and the place of reformulated fuels in refinery product distribution
are covered.
The physical and chemical properties of petroleum and petroleum products
are described, along with major refining processes. Data for determination of

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typical product yields, investment, and operating costs for all major refining processes and for supporting processes are also given.
The investment, operating cost, and utility data given herein are typical
average recent data. As such, this information is suitable for approximating the
economics of various refining configurations. The information is not sufficiently
accurate for definitive comparisons of competing processes.
The yield data for reaction processes have been extended to allow complete
material balances to be made from physical properties. Insofar as possible, data
for catalytic reactions represent average yields for competing proprietary catalysts
and processes.
The material is organized to utilize the case-study method of learning. An
example case-study problem begins in Chapter 4 (Crude Distillation) and concludes in Chapter 18 (Economic Evaluation). The appendices contain basic engineering data and a glossary of refining terms. Valuable literature references are
noted throughout the book.
We have held responsible positions in refinery operation, design, and evaluation, and have taught practical approaches to many refinery problems. This publication relies heavily on our direct knowledge of refining in addition to the expertise shared with us by our numerous associates and peers.
Appreciation is expressed to the many people who contributed data and
suggestions incorporated into this book.
Corporations that have been very helpful include:
Exxon Research and Engineering
Fluor Daniel
Stratco, Inc.
The M. W. Kellogg Company
UOP LLC
Individual engineers who have contributed significant technical information to various editions of this book are listed below:
Robert W. Bucklin
Steve Chafin
D. A. Cheshire
Jack S. Corlew
Gary L. Ewy
P. M. Geren
Andy Goolsbee
Jeff G. Handwerk
Jay M. Killen
Viron D. Kliewer
David R. Lohr

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James R. McConaghy
Jill Meister
James R. Murphy
Marvin A. Prosche
Ed J. Smet
Delbert F. Tolen
Donald B. Trust
William T. War
Diane York
Special credit is due to James K. Arbuckle for his excellent drafting of all
the graphs, Pat Madison, Golden Software Co., for providing the Grapher 2
software to make the cost-curve figures, and Jane Z. Gary, who helped greatly
in improving the clarity of presentation.
James H. Gary
Glenn E. Handwerk

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Contents

Preface
1 INTRODUCTION
1.1
Overall Refinery Flow
2 REFINERY PRODUCTS
2.1
Low-Boiling Products
2.2
Gasoline
2.3
Gasoline Specifications
2.4
Distillate Fuels
2.5
Jet and Turbine Fuels
2.6
Automotive Diesel Fuels
2.7
Railroad Diesel Fuels
2.8
Heating Oils
2.9
Residual Fuel Oils
Notes
3 REFINERY FEEDSTOCKS
3.1
Crude Oil Properties
3.2
Composition of Petroleum
3.3
Crudes Suitable for Asphalt Manufacture
3.4
Crude Distillation Curves
Problems
Notes
4 CRUDE DISTILLATION
4.1
Desalting Crude Oils
4.2
Atmospheric Topping Unit
4.3
Vacuum Distillation

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4.4
4.5
4.6

Auxiliary Equipment
Crude Distillation Unit Products
Case-Study Problem: Crude Units
Problems
Notes

COKING AND THERMAL PROCESSES

5.1
Types, Properties, and Uses of Petroleum Coke
5.2
Process DescriptionDelayed Coking
5.3
OperationDelayed Coking
5.4
Process DescriptionFlexicoking
5.5
Process DescriptionFluid Coking
5.6
Yields from Flexicoking and Fluid Coking
5.7
Capital Costs and Utilities for Flexicoking and Fluid Coking
5.8
Visbreaking
5.9
Case-Study Problem: Delayed Coker
Problems
Notes
Additional Reading
6 CATALYTIC CRACKING
6.1
Fluidized-Bed Catalytic Cracking
6.2
New Designs for Fluidized-Bed Catalytic Cracking Units
6.3
Cracking Reactions
6.4
Cracking of Paraffins
6.5
Olefin Cracking
6.6
Cracking of Naphthenic Hydrocarbons
6.7
Aromatic Hydrocarbon Cracking
6.8
Cracking Catalysts
6.9
FCC Feed Pretreating
6.10 Process Variables
6.11 Heat Recovery
6.12 Yield Estimation
6.13 Capital and Operating Costs
6.14 Case-Study Problem: Catalytic Cracker
Problems
Notes
Additional Reading
7 CATALYTIC HYDROCRACKING
7.1
Hydrocracking Reactions
7.2
Feed Preparation

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7.3
7.4
7.5
7.6
7.7
7.8
7.9

The Hydrocracking Process

Hydrocracking Catalyst
Process Variables
Hydrocracking Yields
Investment and Operating Costs
Modes of Hydrocracker Operation
Case-Study Problem: Hydrocracker
Problems
Notes
Additional Reading

8 HYDROPROCESSING AND RESID PROCESSING

8.1
Composition of Vacuum Tower Bottoms
8.2
Processing Options
8.3
Hydroprocessing
8.4
Expanded-Bed Hydrocracking Processes
8.5
Moving-Bed Hydroprocessors
8.6
Solvent Extraction
8.7
Summary of Resid Processing Operations
Notes
Additional Reading
9 HYDROTREATING
9.1
Hydrotreating Catalysts
9.2
Aromatics Reduction
9.3
Reactions
9.4
Process Variables
9.5
Construction and Operating Costs
9.6
Case-Study Problem: Hydrotreaters
Problems
Notes
10 CATALYTIC REFORMING AND ISOMERIZATION
10.1 Reactions
10.2 Feed Preparation
10.3 Catalytic Reforming Processes
10.4 Reforming Catalyst
10.5 Reactor Design
10.6 Yields and Costs
10.7 Isomerization
10.8 Capital and Operating Costs
10.9 Isomerization Yields

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10.10 Case-Study Problem: Naphtha Hydrotreater, Catalytic

Reformer, and Isomerization Unit
Problems
Notes
Additional Reading
11 ALKYLATION AND POLYMERIZATION
11.1 Alkylation Reactions
11.2 Process Variables
11.3 Alkylation Feedstocks
11.4 Alkylation Products
11.5 Catalysts
11.6 Hydrofluoric Acid Processes
11.7 Sulfuric Acid Alkylation Processes
11.8 Comparison of Processes
11.9 Alkylation Yields and Costs
11.10 Polymerization
11.11 Case-Study Problem: Alkylation and Polymerization
Problems
Notes
12 PRODUCT BLENDING
12.1 Reid Vapor Pressure
12.2 Octane Blending
12.3 Blending for Other Properties
12.4 Case-Study Problem: Gasoline Blending
12.5 Case-Study Problem: Diesel and Jet Fuel Blending
Problems
Notes
Additional Reading
13 SUPPORTING PROCESSES
13.1 Hydrogen Production and Purification
13.2 Gas Processing Unit
13.3 Acid Gas Removal
13.4 Sulfur Recovery Processes
13.5 Ecological Considerations in Petroleum Refining
13.6 Waste Water Treatment
13.7 Control of Atmospheric Pollution
13.8 Noise Level Control
13.9 Case-Study Problem: Saturated Gas Recovery, Amine,
and Sulfur Recovery Units

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Notes
Additional Reading
14 LUBRICATING OIL BLENDING STOCKS
14.1 Lube Oil Processing
14.2 Propane Deasphalting
14.3 Viscosity Index Improvement and Solvent Extraction
14.4 Viscosity Index Improvement and Hydrocracking
14.5 Dewaxing
14.6 Hydrofinishing
14.7 Finishing by Clay Contacting
14.8 Environmental Impacts
Notes
Additional Reading
15 PETROCHEMICAL FEEDSTOCKS
15.1 Aromatics Production
15.2 Unsaturate Production
15.3 Saturated Paraffins
Notes
Additional Reading
16 ADDITIVES PRODUCTION FROM REFINERY
FEEDSTOCKS
16.1 Use of Alcohols and Ethers
16.2 Ether Production Reactions
16.3 Ether Production Processes
16.4 Yields
16.5 Costs for Ether Production
16.6 Production of Isobutylene
16.7 Commercial Dehydrogenation Processes
16.8 Houdrys CATOFIN
16.9 Phillips Petroleums STAR
16.10 UOP LLCs OLEFLEX
16.11 Snamprogetti/Yarsintez Process
16.12 Costs to Produce Isobutylene from Isobutane
16.13 International Union of Pure and Applied Chemists
Nomenclature
Notes
17 COST ESTIMATION
17.1 Rule-of-Thumb Estimates
17.2 Cost-Curve Estimates

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17.3
17.4
17.5
17.6
17.7
17.8
17.9
17.10
17.11

Major Equipment Factor Estimates

Definitive Estimates
Summary Form for Cost Estimates
Storage Facilities
Land and Storage Requirements
Steam Systems
Cooling Water Systems
Other Utility Systems
Application of Cost Estimation Techniques
Problems
Notes

18 ECONOMIC EVALUATION
18.1 Definitions
18.2 Return on Original Investment
18.3 Payout Time
18.4 Discounted Cash Flow Rate of Return
18.5 Case-Study Problem: Economic Evaluation
18.6 Case-Study Problem: Economic Solution
Problems
Notes
APPENDICES
A Definitions of Refining Terms
B Physical Properties
C U.S. Bureau of Mines Routine Analyses of Selected
Crude Oils
D Economic Evaluation Example Problem
Notes
E Photographs

Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved.