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Chief Editor Hiroo Tominaga Professor Emeritus University of Tokyo Masakazu Tamaki Chairman Chiyoda Corporation Editors This edition was produced by the following editors from Chiyoda. Yasuo Morimura Munekazu Nakamura Hideki Hashimoto Yoshimi Shiroto Koji Watanabe Masato Tauchi Takafumi Kuriyama Ak...

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Chief Editor Hiroo Tominaga

Masakazu Tamaki

Professor Emeritus University of Tokyo Chairman Chiyoda Corporation

Editors This edition was produced by the following editors from Chiyoda.

Yasuo Morimura Munekazu Nakamura Hideki Hashimoto Yoshimi Shiroto Koji Watanabe Masato Tauchi Takafumi Kuriyama Akio Shindo

Resid Fluid Catalytic Cracking (RFCC) Unit (By courtesy ofTohoku Oil Co., Ltd. Licenced by The M.W. Kellog Company)

Resid Hydrodesulfurization with Onstream Catalyst Replacement (OCR) Unit (By courtesy of ldemitu Kosan Co., Ltd. Licenced by Chevron Products Company Technology Marketing)

Catalysts for Hydroprocessing (By courtesy of Nippon Ketjen Co.• Ltd.)

Industrial Catalyst Types (By courtesy of Sued Cbemie AG & Nissan Girdler Catalyst Co .• Ltd)

Chemical Reaction and Reactor Design Edited by

HIROO TOMINAGA Professor Emeritus. University of Tokyo. Japan

and

MASAKAZU TAMAKI Chairman , Chiyoda Corporation. Yokohama. Japan

JOHN WILEY & SONS Chichester· New York · Weinheim ·Brisbane · Singapore · Toro nto

Authorized Translation from Japanese language edition published by Maruzen Co., Ltd, Tokyo Copyright© 1997 John Wiley & Sons, Ltd. Baffins Lane, Chichester, West Sussex P019 IUD, England National 01243 779777 International ( + 44) 1243 779777 e-mail (for orders and customer service enquiries): [email protected] Visit our Home Page on http:jjwww.wiley.co.uk or http://www.wiley.com All Rights Reserved. No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency, 90 Tottenham Court Road, London, UK WIP 9HE, UK, without the permission in writing of the Publisher. Published under the Co-publishing Agreement between Wiley and Maruzen, the English translation published by John Wiley and Sons Ltd, Chichester.

Other Wiley Editorial Offices John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, USA VCH Verlagsgesellschaft mbH. Pappelallee 3, D-69469 Weinheim, Germany Jacaranda Wiley Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Rexdale, Ontario M9W I LI, Canada

British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0-471-97792-6 Typeset by Dobbie Typesetting Limited, Tavistock. Devon Printed and bound by Antony Rowe Ltd. Eastboume

Contents

Preface to the English Edition Preface . . . . . . . . . . .

ix xi

Chapter 1 Chemical Reactions and Design of Chemical Reactors Hiroo Tominaga . . . . . . . . . . . . . . . . .

1.1 1.2 1.3 1.4 1.5

Introduction . . . . . . . . . . . . . . . . Science and Engineering for Reactor Design . Theory of Chemical Reaction . . . . . . . . Chemical Reaction Engineering and Reactor Design Reactor Design for Industrial Processes 1.5.1 Naphtha Cracking . . . . 1.5.2 Tubular Steam Reforming 1.5.3 Epoxy Resin Production . 1.5.4 Hydrotreating . . . . . . 1.5.5 Fluid Catalytic Cracking . 1.5.6 Flue Gas Desulphurization .

Chapter 2 Equilibrium and Reaction Rate Hiroshi Komiyama . . . . . . . . . . .

2.1

Nature of Chemical Reaction . . . . 2.1.1 Supply of Activation Energy . 2.1.2 Elementary and Complex Reactions. 2.1.3 Other Factors in Reactor Design . . 2.2 Direction of the Reaction Progress and Chemical Equilibrium 2.2.1 Direction of the Reaction Progress . . 2.2.2 Role of the Catalyst . . . . . . . . . . . . 2.2.3 Reversible and Irreversible Reactions . . . . 2.2.4 How to Calculate the Heat of Reaction and the Equilibrium Constant . . . . . . . . 2.2.5 Operating Conditions and Energy Efficiency of Chemical Reactions . . . . . . . . . . . .

1

1 2 3 8 8 9 11

12 13 14

17 17 17 18 19 21 21 22 24 25 26

CONTENTS

vi 2.3 The Rate of Reaction . . . . . . . . . . . . . 2.3.1 Factors Governing the Rate of Reaction . 2.4 Complex Reaction System . . . . . . 2.4. I Rate-determining Step . . . . . . . . . 2.4.2 Patterning of Reaction Systems . . . . 2.4.3 Relations with Other Transfer Processes Chapter 3 Fundamentals of Heat and Mass Transfer Koichi Asano . . . . . . . . . .

3.1

3.2

3.3

3.4

3.5

3.6

Rate Equations . . . . . . 3.1.1 Conduction of Heat . 3.1.2 Diffusion . . . . . . 3.1.3 Diffusion Flux and Mass Flux . Mass and Heat Transfer Coefficients . 3.2.1 Mass Transfer Coefficient . . . 3.2.2 Overall Mass Transfer Coefficient 3.2.3 Heat Transfer Coefficient . . . . 3.2.4 Overall Heat Transfer Coefficient. Heat and Mass Transfer in a Laminar Boundary Layer along a Flat Plate . . . . . . . . . . . . . . . . . 3.3.1 Governing Equations of Heat and Mass Transfer. 3.3.2 Physical Interpretation of the Dimensionless Groups used in Heat and Mass Transfer Correlation . . 3.3.3 Similarity Transformation . . . . . . . . . . . . 3.3.4 Numerical Solutions for Heat and Mass Transfer . 3.3.5 High Mass Flux Effect. . . . . . . . . . . . . Heat Transfer inside a Circular Tube in Laminar Flow 3.4.1 Heat Transfer inside a Circular Tube with Uniform Velocity Profile. . . . . . . . . . 3.4.2 Heat Transfer inside a Circular Tube with Parabolic Velocity Profile (Graetz problem) Mass Transfer of Bubbles, Drops and Particles . 3.5. I Hadamard Flow. . . . . . . . . . . . . . . 3.5.2 Evaporation of a Drop in the Gas Phase . . . 3.5.3 Continuous Phase Mass Transfer of Bubbles or Drops in the Liquid Phase. . . . . . . . . . 3.5.4 Dispersed Phase Mass Transfer . . . . . . . . 3.5.5 Heat and Mass Transfer of a Group of Particles and the Void Function. Radiant Heat Transfer . . . . . . . . . . . . . . . . 3.6.1 Heat Radiation . . . . . . . . . . . . . . . . 3.6.2 Governing Equations of Radiant Heat Transfer.

28 30 36 36 38 38

39 39 39 40 42 43 43 44 48 48 49 49 50 52 53 55 56 57 58 59 59 60 62 62 63 65 65 66

vii

CONTENTS

Chapter 4

Fundamentals of Reactor Design. . . . . . . . . . . . . .

Reactor Types and Their Applications Shintaro Furusaki . . . . . . . 4.1.1 Homogeneous Reactors . . 4.1.2 Heterogeneous Reactors . . 4.2 Design of Homogeneous Reactors Yukihiro Shimogaki . . . . . . . . 4.2.1 Material and Heat Balances in Reaction Systems 4.2.2 Design of Batch Stirred Tank Reactor . . . 4.2.3 Design of Continuous Stirred Tank Reactors . . 4.2.4 Design of Tubular Reactors . . . . . . . . . . 4.2.5 Homogeneous and Heterogeneous Complex Reactions. 4.3 Planning and Design of M ultiphase Reactors Masayuki Horio . . . . . . . . . . . . . . . . . . . 4.3.1 Features of Planning and Design of Multiphase Reaction Processes . . . . . . . . . . . . 4.3.2 Model Description of Multiphase Processes . . . 4.3.3 Concepts of Multiphase Reaction Processes . . . 4.3.4 Development and Scale-up of Multiphase Reactors 4.4 Dynamic Analysis of Reaction System Hisayoshi Matsuyama. . . . 4.4.1 Dynamics of Reactors 4.4.2 Stability of Reactors . 4.4.3 Control of Reactors . 4.4.4 Optimization of Reactor Systems .

69

4.1

Chapter 5

Design of an Industrial Reactor

Naphtha Cracking Hiroshi Yagi . . . . . . . . . . . . 5.1.1 Petrochemical Complex in Japan . 5.1.2 Cracking Furnace for Naphtha. 5.1.3 Treatment of a Cracked Gas . . . 5.1.4 Quench and Heat Recovery. . . . 5.1.5 Thermodynamics of Thermal Cracking Reaction 5.1.6 Mechanism of Thermal Cracking . . . . 5.1. 7 Reaction Model for Yield Estimation . . 5.1.8 Design Procedure of Cracking Furnace . 5.1.9 Results of Thermal Cracking Simulation 5.1.10 Technology Trend of a Cracking Furnace. 5.2 Tubular Steam Reforming J. R. Rostrup-Nielsen and Lars J. Christiansen 5.2.1 The Reactions . . . . . 5.2.2 The Tubular Reformer . . . . . . . .

71 71 74 83 83 84 91 94 97 105 I05 108 135 170 183 183 185 188 194 211

5.1

213 213 217 221 222 224 226 230 236 239 243 247 248 252

viii

CONTENTS

The Catalyst and Reaction Rate . Poisoning . . . . . . . . . . . . Carbon Formation . . . . . . . C0 2 Reforming . . . . . . . . . Reforming of High Hydrocarbons Alternatives to Steam Reforming Technology. Epoxy Resin Production Goro Soma and Yasuo Hosono . . . . . . 5.3.1 Epoxy Resin . . . . . . . . . . . 5.3.2 Quality Parameters of Epoxy Resin 5.3.3 Elementary Reactions for Epoxy Resin Production . 5.3.4 Epoxy Resin Production Processes . 5.3.5 Process Operating Factors . 5.3.6 The Reaction Model. . . . . . . . 5.3.7 Batch Operation. . . . . . . . . . 5.3.8 Simulation Using the Reaction Model 5.3.9 Design of the First-stage Reactor . . 5.3.10 Design of the Second-stage Reactor. Hydrotreating Reactor Design Alan G. Bridge and E. Morse Blue 5.4.1 Hydrotreating Objectives. . 5.4.2 Process Fundamentals . . . 5.4.3 VGO Hydrotreating Reactions . 5.4.4 VGO Hydrotreating Catalysts . 5.4.5 VGO Hydrotreating Process Conditions 5.4.6 VGO Hydrotreating Reactor Design . . 5.4. 7 VGO Hydro treating Operation. . . . . 5.4.8 VGO Hydrotreating Safety Procedures. 5.4.9 Future Trends. . . . . . . . Fluid Catalytic Cracking Toru Takatsuka and Hideki Minami. 5.5.1 Outline of the FCC Process . 5.5.2 Basic Theory of Fluid Catalytic Cracking. 5.5.3 Theoretical Discussion of FCC Reactor Design . 5.5.4 Practice of FCC Reactor Design. . . . . . . . . . . 5.5.5 Material Balance and Heat Balance around Reactors . Wet Flue Gas Desulphurization Hiroshi Yanagioka and Teruo Sugiya 5.6.1 Process Description . . . . . 5.6.2 Structure of JBR . . . . . . 5.6.3 Chemical Reactions in JBR . . . . . . . . . . 5.6.4 Heat and Material Balance around the Reactor. 5.6.5 Reactive Impurities in the Flue Gas . . . . . 5.6.6 Applicable Materials for the Wet FGD Plant . Index . . . . . . ...

5.2.3 5.2.4 5.2.5 5.2.6 5.2.7 5.2.8 5.3

5.4

5.5

5.6

• • • • •

0

•

259 262 264 267 269 269 273 273 274 275 276 279 281 282 283 285 292 297 298 304 310 314 317 317 328 331 332 335 339 345 352 365 369

377 378 380 381 388 391 393 395

Preface to the English Edition

Now that the Cold War is over, the next hurdle for mankind is the wealth gap between north and south. We must cooperate with developing countries to generate sustainable development programmes that bring true prosperity while protecting the environment. The engineers in engineering firms hope that the chemical engineering skills they refine daily will contribute to international economic development and to richer lives for all mankind. We believe engineering stands alongside agriculture, commerce, and manufacturing as one of the four pillars of national strength. These four words are engraved in the pedestals of the four columns of the Albert Memorial in London, which was built in 1876 when the British Empire was at its zenith. And these four words connote the source of Britain's tremendous strength during the reign of Queen Victoria. Chemical Reaction and Reactor Design commemorates the 50th anniversary of the foundation of the Chiyoda Corporation, and was published in Japanese by Maruzen Co., Ltd in January 1996. This book was created for colleagues in the design departments of engineering companies, and for students who hope to pursue careers in engineering. The Japanese edition immediately prompted many requests for an English version. Now, thanks to John Wiley & Sons Ltd, the English edition is available. In the course of their daily work, chemical engineers come in contact with various reactions, catalysts, and reactors. They constantly encounter new technologies, such as residue fluidized catalytic cracking (RFCC), continuous catalyst recirculation (CCR) reforming and heat exchanger type reactors and consistently meet the challenge of using them effectively. This experience helps them to unify systems and equipment into a smoothly operating entity, achieving greater precision in design standards and more efficient design systems for better operation of reactors, separators, heat exchangers, and other hardware. Systems and equipment operate as an organic whole in petroleum refining, petrochemical processes, and environmental protection procedures, combining many individual processes at very high levels of precision. These processes are vital to industry because so many manufacturers use them. In the first four chapters, Chemical Reaction and Reactor Design deals with the fundamentals of chemical engineering. Then it gives six case studies in reaction and reactor design in Chapter 5.

X

PREFACE TO THE ENGLISH EDITION

We hope this book will make it possible to develop reliable reactors without relying on expensive, time-consuming tests with pilot or bench plants. Dr Hiroo Tominaga, professor emeritus at the University of Tokyo, supervised the editing of the book and wrote the first chapter. Dr Shintaro Furusaki, a professor at the University of Tokyo, along with other authorities in the field, wrote the sections on basic theory. The sections of Chapter 5 that deal with tubular steam reforming, hydrotreating, and polymerization, were prepared in cooperation with licensors of the applicable technologies, i.e., Haldor Tops0e A/S of Denmark, Chevron Research and Technology Company of the United States, and Asahi Denka Kogyo K.K. of Japan. The other sections of Chapter 5 were written and edited by Chiyoda Corporation engineers. We wish to thank the many companies that provided invaluable assistance for this book, and Maruzen Co., Ltd and John Wiley & Sons Ltd, without whose help and cooperation it could never have been published. I hope and believe that this English version will help the technological development of reaction engineering and reactor design worldwide and serve as a springboard to bigger and better things for individual engineers. March 1997, Masakazu Tamaki

Preface

This book presents a wealth of knowledge on reaction kinetics and its application to chemical reactor design and operation; and intended as a text for students in technical college and graduate school, and also for scientists and engineers engaged in chemical research and development. In the second half of the twentieth century, the chemical industry has made remarkable progress based on the developments of petroleum chemistry and polymer science, representing the innovations in both chemical process and product, respectively. Recently, a deliberate shift in paradigm from process to product innovation seems to be emphasized in the chemical industry. Since no chemical product can be manufactured without a properly designed process to produce it, the significance of process innovation should also be noted. In this connection, reactor design and its operation, which both play a key role in the chemical process, may be considered the key to chemical technology. Perfection of chemical reactor design may be realized based upon the relevant science and engineering. The scientific approach to understanding chemical reaction kinetics and mechanism, however, is now mostly concerned with a simple reaction in order to identify the basic principles in terms of molecular dynamics. On the other hand, chemical reaction engineering aims at computations of a complex system, involving a large number of variables not only of chemistry but also of mass and heat transfer, to select the reactor type, to determine its size and to optimize its operation. There remains much, however, to be supplemented by technical know-how obtained through experience in practice, some of which will be generalized, systematized and integrated as engineering science for reactor design in future. This book is comprised of two parts; reviews of science and engineering as bases· for chemical reactor design; and several examples of specific reactor design practised in petroleum refining, petroleum chemistry, polymer industry or air pollution abatement. All of these are contributed by experts in the related academic discipline or industry. The editors take sole responsibility for any shortcomings in this volume, but hope it will stimulate new ideas in academia and technical advances in industry. We are indebted to the Chiyoda Corporation, Maruzen Co. Ltd., and John Wiley & Sons Ltd for their continued support and encouragement in the publishing of this book. March 1997, Hiroo Tominaga

1 Chemical Reactions and Design of Chemical Reactors

CHAPTER

HIROO TOMINAGA University of Tokyo, Japan

1.1

INTRODUCTION

The Chemical industry is a branch of the industry that produces highly valueadded chemicals from a variety of natural resources used as basic raw materials. Science and technology in the chemical industry centre around the chemical transformation of materials, i.e. chemical reaction, and therefore the design and operation of chemical reactors as ways and means of realizing the chemical reaction, are so important that they may be said to be the key technology of the chemical industry. Theoretical approaches to the design of chemical reactors have thus been developed systematically, utilizing the knowledge of science and engineering about chemical reactions. However, it is not well known to the public how the theories are put into practice by chemical engineers. The book summarizes the fundamental theory of reactor design and the practice of its applications in the industrial processes, such as petroleum refining, petroleum chemistry and others. The book is largely divided into two parts: the fundamentals in Chapters 2-4, and the applications in Chapter 5. This chapter outlines the scope of respective chapters as an introduction to chemical reactions and reactor design.

1.2 SCIENCE AND ENGINEERING FOR REACTOR DESIGN The science and engineering related to reactor design are shown in Figure 1.1, demonstrating how diversified knowledge and information are essential to the design and operation of chemical reactors. Among these, the Chemical Reaction and Reactor Design. Edited by H. Tominaga and M. Tamaki © 1998 John Wiley & Sons Ltd.

H. TOMINAGA

2

fundamental chapters deal with chemical reactions and reaction engineering theories.

1.3 THEORY OF CHEMICAL REACTION This theme is treated in Chapter 2. Why and how does a chemical reaction take place? What factors govern the selectivity and the rate of reaction? The specific field of science dealing with these issues is termed as the theory of chemical reaction, which is comprised of chemical equilibrium, kinetics and mechanisms. The equilibrium of chemical reactions is discussed by chemical thermodynamics, which reveals whether a given chemical reaction will take place or not and if so, to what extent. In more detail, the change in standard free energy of formation accompanied by a chemical reaction gives an equilibrium constant at a given temperature, which provides the equilibrium conversion of !Chemical Reaction

Quantum Chemistry } Molecular Slnleture

Theoryl Collision Theory

Elementary Reaction Process or Chemical Kinetics

Molecular Dynamics

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