PETROLEUM REFINING Technology and Economics Fifth Edition PDF

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PETROLEUM REFINING Technology and Economics Fifth Edition James H. Gary Glenn E. Handwerk Mark J. Kaiser Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton,...

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PETROLEUM REFINING

Technology and Economics Fifth Edition

James H. Gary Glenn E. Handwerk Mark J. Kaiser

Boca Raton London New York

CRC Press is an imprint of the Taylor & Francis Group, an informa business

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CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2007 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-10: 0-8493-7038-8 (Hardcover) International Standard Book Number-13: 978-0-8493-7038-0 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Gary, James H., 1921Petroleum refining : technology and economics. -- 5th ed. / James H. Gary and Mark J. Kaiser. p. cm. Includes bibliographical references and index. ISBN-13: 978-0-8493-7038-0 (acid-free paper) ISBN-10: 0-8493-7038-8 (acid-free paper) 1. Petroleum--Refining. I. Kaiser, Mark J. II. Title. TP690.G33 2007 665.5’38--dc22 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com

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Dedication Glenn E. Handwerk September 4, 1924 to February 29, 2004

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Table of Contents Preface.................................................................................................................... xvii Acknowledgments................................................................................................... xix Authors.................................................................................................................... xxi Chapter 1 1.1 1.2 1.3 1.4

1.5

1.6

1.7

Introduction .......................................................................................... 1

Refinery Processes and Operations ................................................................. 2 Historic Overview ............................................................................................ 4 Product Demand and Supply ........................................................................... 5 U.S. Statistics ................................................................................................... 7 1.4.1 Capacity................................................................................................ 7 1.4.2 Capacity Creep..................................................................................... 7 1.4.3 Utilization............................................................................................. 7 1.4.4 Industry Structure................................................................................. 8 1.4.5 Regional Specialization........................................................................ 9 World Statistics .............................................................................................. 12 1.5.1 Product Demand................................................................................. 12 1.5.2 Capacity.............................................................................................. 12 1.5.3 Configuration, Complexity, and Yield ............................................... 12 1.5.4 Investment Patterns ............................................................................ 15 Industry Characteristics.................................................................................. 16 1.6.1 Each Refinery Is Unique.................................................................... 16 1.6.2 No Two Crude Oils Are the Same..................................................... 16 1.6.3 Refinery Configuration Evolves over Time....................................... 17 1.6.4 Not All Refineries Are Created Equal ............................................... 17 1.6.5 Refineries Are Capital-Intensive, Long-Lived, Highly Specific Assets ....................................................................... 18 1.6.6 Refined Products Are Commodities .................................................. 18 1.6.7 Refined Products Are Sold in Segment Markets............................... 18 1.6.8 Product Prices Are Volatile ................................................................ 18 1.6.9 Product Prices Are Correlated to Crude Oil Prices .......................... 19 1.6.10 Refineries Are Price Takers ............................................................... 19 1.6.11 Gravity Down, Sulfur Up .................................................................. 19 1.6.12 Refining Optimization Involves Multiple Trade-Offs ....................... 20 1.6.13 Petroleum Refining Is Energy Intensive............................................ 20 1.6.14 Refining Operations and Products Impact the Environment............. 21 Refinery Economics ....................................................................................... 21 1.7.1 Refinery Economics Is Complicated ................................................. 21 1.7.2 Data Source ........................................................................................ 21 v

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1.7.3 Boom and Bust Industry.................................................................... 22 1.7.4 Refining Margins................................................................................ 22 1.7.5 Investment Decision Making ............................................................. 22 1.8 Cost Estimation .............................................................................................. 23 1.8.1 Data Sources ...................................................................................... 23 1.8.2 Process Technologies ......................................................................... 24 1.8.3 Function Specification ....................................................................... 25 1.8.4 Utility Requirements .......................................................................... 25 1.8.4.1 Normalization ..................................................................... 26 1.8.5 Nelson-Farrar Cost Indices ................................................................ 27 1.8.6 Limitations of Analysis...................................................................... 27 1.9 Refinery Complexity ...................................................................................... 28 1.9.1 Data Source ........................................................................................ 28 1.9.2 Unit Complexity................................................................................. 29 1.9.3 Refinery Complexity .......................................................................... 29 1.9.4 Example.............................................................................................. 29 1.9.5 Generalized Complexity .................................................................... 30 1.10 Refinery Flow Scheme and Chapter Outline................................................. 32 1.10.1 Refinery Products and Feedstocks (Chapters 2, 3)......................... 32 1.10.2 Crude Distillation (Chapter 4)......................................................... 32 1.10.3 Coking and Thermal Processes (Chapter 5) ................................... 32 1.10.4 Catalytic Cracking (Chapter 6) ....................................................... 33 1.10.5 Catalytic Hydrocracking (Chapter 7) .............................................. 33 1.10.6 Hydroprocessing and Resid Processing (Chapter 8) ...................... 33 1.10.7 Hydrotreating (Chapter 9) ............................................................... 34 1.10.8 Catalytic Reforming and Isomerization (Chapter 10) .................... 34 1.10.9 Alkylation and Polymerization (Chapter 11).................................. 34 1.10.10 Product Blending (Chapter 12) ....................................................... 35 1.10.11 Supporting Processes (Chapter 13) ................................................. 35 1.10.12 Refinery Economics and Planning (Chapter 14) ............................ 35 1.10.13 Lubricating Oil Blending Stocks (Chapter 15)............................... 36 1.10.14 Petrochemical Feedstocks (Chapter 16).......................................... 36 1.10.15 Additives Production from Refinery Feedstocks (Chapter 17) ...... 36 1.10.16 Cost Estimation (Chapter 18).......................................................... 36 1.10.17 Economic Evaluation (Chapter 19) ................................................. 36 Notes ........................................................................................................................ 37 Chapter 2 2.1 2.2 2.3 2.4

Refinery Products............................................................................... 41

Low-Boiling Products .................................................................................... 41 Gasoline.......................................................................................................... 44 Gasoline Specifications .................................................................................. 49 Distillate Fuels ............................................................................................... 51 2.4.1 Jet and Turbine Fuels......................................................................... 51 2.4.2 Automotive Diesel Fuels.................................................................... 53 2.4.3 Railroad Diesel Fuels......................................................................... 53

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2.4.4 Heating Oils ....................................................................................... 53 2.5 Residual Fuel Oils.......................................................................................... 54 Notes ........................................................................................................................ 55 Chapter 3

Refinery Feedstocks ........................................................................... 57

3.1

Crude Oil Properties ...................................................................................... 57 3.1.1 API Gravity ........................................................................................ 58 3.1.2 Sulfur Content, Wt%.......................................................................... 58 3.1.3 Pour Point, °F (°C) ............................................................................ 58 3.1.4 Carbon Residue, Wt%........................................................................ 58 3.1.5 Salt Content, lb/1000 bbl................................................................... 59 3.1.6 Characterization Factors .................................................................... 59 3.1.7 Nitrogen Content, Wt% ..................................................................... 59 3.1.8 Distillation Range .............................................................................. 60 3.1.9 Metals Content, ppm.......................................................................... 60 3.1.10 Total Acid Number............................................................................. 60 3.2 Composition of Petroleum ............................................................................. 62 3.2.1 Paraffins.............................................................................................. 62 3.2.2 Olefins ................................................................................................ 62 3.2.3 Naphthenes (Cycloparaffins).............................................................. 63 3.2.4 Aromatics ........................................................................................... 64 3.3 Crudes Suitable for Asphalt Manufacture ..................................................... 64 3.3.1 Crude Distillation Curves .................................................................. 65 Problems .................................................................................................................. 68 Notes ........................................................................................................................ 68 Additional Reading.................................................................................................. 70 Chapter 4

Crude Distillation............................................................................... 71

4.1 4.2 4.3 4.4 4.5 4.6

Desalting Crude Oils...................................................................................... 71 Atmospheric Topping Unit ............................................................................ 80 Vacuum Distillation ....................................................................................... 84 Auxiliary Equipment...................................................................................... 86 Crude Distillation Unit Products ................................................................... 86 Case-Study Problem: Crude Units................................................................. 88 4.6.1 Statement of the Problem .................................................................. 90 4.6.2 General Procedure.............................................................................. 90 Problems .................................................................................................................. 93 Notes ........................................................................................................................ 95 Chapter 5 5.1 5.2

Coking and Thermal Processes.......................................................... 97

Types, Properties, and Uses of Petroleum Coke ........................................... 97 Process Description—Delayed Coking ......................................................... 99 5.2.1 Coke Removal—Delayed Coking.................................................... 102

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5.3 Operation—Delayed Coking........................................................................ 102 5.4 Process Description—Flexicoking............................................................... 105 5.5 Process Description—Fluid Coking ............................................................ 108 5.6 Yields from Flexicoking and Fluid Coking................................................. 110 5.7 Capital Costs and Utilities for Flexicoking and Fluid Coking ................... 111 5.8 Visbreaking................................................................................................... 111 5.9 Case-Study Problem: Delayed Coker .......................................................... 116 Problems ................................................................................................................ 119 Notes ...................................................................................................................... 120 Additional Reading................................................................................................ 120 Chapter 6

Catalytic Cracking ........................................................................... 121

6.1 Fluidized Bed Catalytic Cracking ............................................................... 122 6.2 New Designs for Fluidized Bed Catalytic Cracking Units......................... 133 6.3 Cracking Reactions ...................................................................................... 134 6.4 Cracking of Paraffins ................................................................................... 135 6.5 Olefin Cracking ............................................................................................ 136 6.6 Cracking of Naphthenic Hydrocarbons ....................................................... 136 6.7 Aromatic Hydrocarbon Cracking ................................................................ 136 6.8 Cracking Catalysts ....................................................................................... 136 6.9 FCC Feed Pretreating .................................................................................. 140 6.10 Process Variables.......................................................................................... 140 6.11 Heat Recovery.............................................................................................. 142 6.12 Yield Estimation........................................................................................... 143 6.13 Capital and Operating Costs........................................................................ 147 6.14 Case-Study Problem: Catalytic Cracker ...................................................... 147 Problems ................................................................................................................ 150 Notes ...................................................................................................................... 153 Additional Reading................................................................................................ 157 Chapter 7 7.1 7.2 7.3 7.4 7.5

7.6 7.7

Catalytic Hydrocracking .................................................................. 161

Hydrocracking Reactions............................................................................. 162 Feed Preparation .......................................................................................... 164 The Hydrocracking Process ......................................................................... 165 Hydrocracking Catalyst................................................................................ 168 Process Variables.......................................................................................... 169 7.5.1 Reactor Temperature ........................................................................ 169 7.5.2 Reactor Pressure............................................................................... 169 7.5.3 Space Velocity ............................................