石油炼制技术和经济petroleum refining-technology and economics.pdf

Marcel Dekker, Inc.New YorkBasel TM Petroleum Refining Technology and Economics Fourth Edition James H. Gary Colorado School of Mines Golden, Colorado Glenn E. Handwerk Consulting Chemical Engineer Golden, Colorado Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved. ISBN 0-8247-0482-7 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel 212-696-9000; fax 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel 41-61-261-8482; fax 41-61-261-8896 World Wide Web The publisher offers discounts on this book when ordered in bulk quantities. For more ination, write to Special Sales/Professional Marketing at the headquarters address above. Copyright  2001 by Marcel Dekker, Inc.All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any or by any means, electronic or mechanical, including photocopying, microfi lming, and recording, or by any ination storage and retri system, without permission in writing from the publisher. Current printing last digit 10 9 8 7 6 5 4 3 2 1 PRINTED IN THE UNITED STATES OF AMERICA Preface Today refi ners are facing investments of billions of dollars in equipment to meet environmental requirements frequently set by political stipulation with little re- gard 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, refi ners 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 reulated fuels that have a mini- mal impact on degradation of the environment. We say ‘‘short-term’’ because laws have already been passed stipulating that within the next two decades hydro- carbon fuel will not be acceptable and only totally nonpolluting fuels will be acceptable. At the present time the only nonpolluting fuels specifi ed are solar and electric energy and hydrogen. This allows only a short time for the petroleum industry torecover the largeinvestment required to meet the presentlegal require- ments. 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 effi ciency. 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 op- tions and the processing equipment required in a modern refi nery. The basic aspects of current petroleum-refi ning technology and economics are presented in a systematic manner suitable for ready reference by technical managers, practicing engineers, university faculty members, and graduate or se- nior students in chemical engineering. In addition, the environmental aspects of refi nery fuels and the place of reulated fuels in refi nery product distribution are covered. The physical and chemical properties of petroleum and petroleum products are described, along with major refi ning processes. Data for determination of iii ivPreface typical product yields, investment, and operating costs for all major refi ning pro- cesses and for supporting processes are also given. The investment, operating cost, and utility data given herein are typical average recent data. As such, this ination is suitable for approximating the economics of various refi ning confi gurations. The ination is not suffi ciently accurate for defi nitive 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 forcatalytic reactionsrepresent average yieldsforcompeting proprietarycatalysts and processes. The material is organized to utilize the case-study of learning. An example case-study problem begins in Chapter 4 Crude Distillation and con- cludes in Chapter 18 Economic uation. The appendices contain basic engi- neering data and a glossary of refi ning terms. Valuable literature references are noted throughout the book. We have held responsible positions in refi nery operation, design, and u- ation, and have taught practical approaches to many refi nery problems. This pub- lication relies heavily on our direct knowledge of refi ning in addition to the exper- tise 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 signifi cant technical ina- tion to various editions of this book are listed below Robert W. Bucklin Steve Chafi n 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 Prefacev 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 fi gures, and Jane Z. Gary, who helped greatly in improving the clarity of presentation. James H. Gary Glenn E. Handwerk Contents Prefaceiii 1INTRODUCTION1 1.1 Overall Refi nery Flow3 2REFINERY PRODUCTS5 2.1Low-Boiling Products6 2.2Gasoline9 2.3 Gasoline Specifi cations13 2.4Distillate Fuels16 2.5Jet and Turbine Fuels16 2.6Automotive Diesel Fuels17 2.7Railroad Diesel Fuels18 2.8Heating Oils19 2.9Residual Fuel Oils20 Notes20 3REFINERY FEEDSTOCKS21 3.1Crude Oil Properties22 3.2Composition of Petroleum26 3.3Crudes Suitable for Asphalt Manufacture30 3.4Crude Distillation Curves30 Problems35 Notes35 4CRUDE DISTILLATION37 4.1Desalting Crude Oils37 4.2Atmospheric Topping Unit50 4.3Vacuum Distillation51 vii viiiContents 4.4Auxiliary Equipment57 4.5Crude Distillation Unit Products58 4.6Case-Study Problem Crude Units58 Problems62 Notes66 5COKING AND THERMAL PROCESSES67 5.1Types, Properties, and Uses of Petroleum Coke68 5.2Process DescriptionDelayed Coking71 5.3OperationDelayed Coking73 5.4Process DescriptionFlexicoking79 5.5Process DescriptionFluid Coking81 5.6Yields from Flexicoking and Fluid Coking82 5.7Capital Costs and Utilities for Flexicoking and Fluid Coking83 5.8Visbreaking83 5.9Case-Study Problem Delayed Coker88 Problems91 Notes91 Additional Reading92 6CATALYTIC CRACKING93 6.1Fluidized-Bed Catalytic Cracking94 6.2New Designs for Fluidized-Bed Catalytic Cracking Units105 6.3Cracking Reactions106 6.4 Cracking of Paraffi ns107 6.5 Olefi n Cracking108 6.6Cracking of Naphthenic Hydrocarbons108 6.7Aromatic Hydrocarbon Cracking108 6.8Cracking Catalysts109 6.9FCC Feed Pretreating112 6.10Process Variables114 6.11Heat Recovery116 6.12Yield Estimation117 6.13Capital and Operating Costs123 6.14Case-Study Problem Catalytic Cracker124 Problems127 Notes134 Additional Reading135 7CATALYTIC HYDROCRACKING137 7.1Hydrocracking Reactions139 7.2Feed Preparation141 Contentsix 7.3The Hydrocracking Process142 7.4Hydrocracking Catalyst146 7.5Process Variables146 7.6Hydrocracking Yields148 7.7Investment and Operating Costs153 7.8Modes of Hydrocracker Operation153 7.9Case-Study Problem Hydrocracker154 Problems156 Notes157 Additional Reading158 8HYDROPROCESSING AND RESID PROCESSING159 8.1Composition of Vacuum Tower Bottoms160 8.2Processing Options162 8.3Hydroprocessing162 8.4Expanded-Bed Hydrocracking Processes165 8.5Moving-Bed Hydroprocessors167 8.6Solvent Extraction167 8.7Summary of Resid Processing Operations170 Notes172 Additional Reading173 9HYDROTREATING175 9.1Hydrotreating Catalysts177 9.2Aromatics Reduction178 9.3Reactions180 9.4Process Variables181 9.5Construction and Operating Costs182 9.6Case-Study Problem Hydrotreaters183 Problems185 Notes186 10CATALYTIC REING AND ISOMERIZATION189 10.1Reactions190 10.2Feed Preparation196 10.3Catalytic Reing Processes196 10.4Reing Catalyst199 10.5Reactor Design201 10.6Yields and Costs202 10.7Isomerization204 10.8Capital and Operating Costs208 10.9Isomerization Yields209 xContents 10.10Case-Study Problem Naphtha Hydrotreater, Catalytic Reer, and Isomerization Unit210 Problems210 Notes213 Additional Reading214 11ALKYLATION AND POLYMERIZATION215 11.1Alkylation Reactions215 11.2Process Variables218 11.3Alkylation Feedstocks219 11.4Alkylation Products220 11.5Catalysts221 11.6 Hydrofl uoric Acid Processes222 11.7Sulfuric Acid Alkylation Processes226 11.8Comparison of Processes230 11.9Alkylation Yields and Costs231 11.10Polymerization231 11.11Case-Study Problem Alkylation and Polymerization239 Problems240 Notes241 12PRODUCT BLENDING243 12.1Reid Vapor Pressure244 12.2Octane Blending248 12.3Blending for Other Properties249 12.4Case-Study Problem Gasoline Blending253 12.5Case-Study Problem Diesel and Jet Fuel Blending256 Problems257 Notes259 Additional Reading259 13SUPPORTING PROCESSES261 13.1 Hydrogen Production and Purifi cation261 13.2Gas Processing Unit266 13.3Acid Gas Removal269 13.4Sulfur Recovery Processes273 13.5 Ecological Considerations in Petroleum Refi ning278 13.6Waste Water Treatment279 13.7Control of Atmospheric Pollution280 13.8Noise Level Control281 13.9Case-Study Problem Saturated Gas Recovery, Amine, and Sulfur Recovery Units281 Contentsxi Notes284 Additional Reading285 14LUBRICATING OIL BLENDING STOCKS287 14.1Lube Oil Processing289 14.2Propane Deasphalting289 14.3Viscosity Index Improvement and Solvent Extraction292 14.4Viscosity Index Improvement and Hydrocracking296 14.5Dewaxing296 14.6 Hydrofi nishing301 14.7Finishing by Clay Contacting301 14.8Environmental Impacts302 Notes302 Additional Reading302 15PETROCHEMICAL FEEDSTOCKS303 15.1Aromatics Production303 15.2Unsaturate Production313 15.3 Saturated Paraffi ns316 Notes316 Additional Reading317 16ADDITIVES PRODUCTION FROM REFINERY FEEDSTOCKS319 16.1Use of Alcohols and Ethers319 16.2Ether Production Reactions321 16.3Ether Production Processes322 16.4Yields325 16.5Costs for Ether Production325 16.6Production of Isobutylene325 16.7Commercial Dehydrogenation Processes327 16.8Houdry’s CATOFIN329 16.9Phillips Petroleum’s STAR329 16.10UOP LLC’s OLEFLEX330 16.11Snamprogetti/Yarsintez Process330 16.12Costs to Produce Isobutylene from Isobutane330 16.13International Union of Pure and Applied Chemists Nomenclature331 Notes331 17COST ESTIMATION333 17.1Rule-of-Thumb Estimates333 17.2Cost-Curve Estimates333 xiiContents 17.3Major Equipment Factor Estimates334 17.4 Defi nitive Estimates335 17.5Summary for Cost Estimates335 17.6Storage Facilities335 17.7Land and Storage Requirements336 17.8Steam Systems337 17.9Cooling Water Systems337 17.10Other Utility Systems337 17.11Application of Cost Estimation Techniques340 Problems353 Notes354 18ECONOMIC UATION355 18.1 Defi nitions355 18.2Return on Original Investment356 18.3Payout Time357 18.4Discounted Cash Flow Rate of Return357 18.5Case-Study Problem Economic uation361 18.6Case-Study Problem Economic Solution365 Problems367 Notes368 APPENDICES A Defi nitions of Refi ning Terms369 BPhysical Properties387 CU.S. Bureau of Mines Routine Analyses of Selected Crude Oils401 DEconomic uation Example Problem417 Notes420 EPhotographs421 Index437 1 Introduction Modern refi nery operations are very complex and, to a person unfamiliar with the industry, it seems to be an impossible task to reduce the complexity to a coordinated group of understandable processes. It is the purpose of this book to present the refi nery processes, as far as possible, in the same order in which the crude fl ows through the refi nery in order to show the purposes and interrelation- ships of the processing units. The case-study is best for quick understand- ing and we recommend that a crude oil be selected and yield and cost calculations be made as the refi ning processes are studied in order. An example problem is given in Chapter 17 for a refi nery of low complexity and the example problem starting in Chapter 4 and ending in Chapter 18 presents a complex refi nery typical of today’s operations. The typical fuels refi nery has as a goal the conversion of as much of the barrel of crude oil into transportation fuels as is economically practical. Although refi neries produce many profi table products, the high-volume profi table products are the transportation fuels gasoline, diesel and turbine jet fuels, and the light heating oils, No. 1 and No. 2. These transportation fuels have boiling points between0 and345C 30to650F. Light heating oils arenot properlytransporta- tion fuels but the hydrocarbon components are interchangeable with those of diesel and jet fuels, only the additives are different. Although products such as lubricating oils, refrigeration and transer oils, and petrochemical feedstocks are profi table, they amount to less than 5 percent of the total crude oil charged to U.S. refi neries. The process fl ow and products for a complete refi nery of high complexity are shown in Figure 1.1. See also Photo 1, Appendix E. The processing equip- ment indicated is for processing crude oils of average gravities and sulfur con- tents. Crude oils with low API gravities high specifi c gravities and high sulfur contents require additional hydrotreating equipment. The quality of crude oils processed by U.S. refi neries is expected to worsen slowly in the future with the sulfur contents and densities to increase. The greater 1 2Chapter 1 Figure 1.1 Refi nery fl ow diagram. Introduction3 densities will mean more of the crude oil will boil above 566C 1050F. Histori- cally this high-boiling material or residua has been used as heavy fuel oil but the demand for these heavy fuel oils has been decreasing because of stricter environmental requirements. This will require refi neries to process the entire bar- rel of crude rather than just the material boiling below 1050F 566C. Sulfur restrictions on fuels coke and heavy fuel oils will affect bottom-of-the-barrel processing as well. These factors will require extensive refi nery additions and modernization and the shift in market requirements among gasolines and re- ulated fuels for transportation will challenge catalyst suppliers and refi nery engineers to develop innovative solutions to these problems. The environmental impacts of fuel preparation and consumption will re- quire that a signifi cant shift take place in product distribution i.e., less conven- tion