Table Of Content

Handbook of Chlor-Alkali Technology Handbook of Chlor-Alkali Technology Volume I: Fundamentals Thomas F. O'Brien Independent Consultant Media, Pennsylvania Tilak V. Bommaraju Independent Consultant Grand Island, New York and Fumio Hine Professor Emeritus Nagoya Institute of Technology Nagoya, Japan ^ Spri ringer Library of Congress Cataloging-in-Publication Data O'Brien, Thomas, 1934- Handbook of chlor-alkali technology/Thomas F. O'Brien, Tilak V. Bommaraju, Fumio Hine. p. cm. Includes bibliographical references and index. ISBN 0-306-48618-0 (v. 1) — ISBN 0-306-48649-9 (v. 2) — ISBN 0-306-48620-2 (v. 3) — ISBN 0-306-48621-0 (v. 4) — ISBN 0-306-48622-9 (v. 5) — ISBN 0-306-48623-7 (indivisible set) — ISBN 0-306-48624-5 (eBook) 1. Chlorine industry—Handbooks, manuals, etc. 2. Alkali industry and trade—Handbooks, manuals, etc. 3. Electrochemistry, Industrial—Handbooks, manuals, etc. I. Bommaraju, Tilak V. II. Hine, Fumio. III. Title. TP245.C5034 2005 2004051611 ISBN: 0-306-48618-0 elSBN: 0-306-48624-5 Set ISBN: 0-306-48623-7 ©2005 Springer Science+Business Media, Inc. All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer Science+Business Media, Inc., 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use in this publication of trade names, trademarks, service marks and similar terms, even if they are not identified as such, is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. Printed in the United States of America 9 8 7 6 5 4 3 2 1 springeronline.com Foreword It is surprising that we had to wait so long for a new book that gives a comprehensive treatment of chlor-alkali manufacturing technology. Technologists are largely still mak ing do with the classical book edited by Sconce, but that is more than thirty years old. At the time of its publication, metal anodes were just beginning to appear, and ion-exchange membrane technology was confined to laboratories. The various encyclopedias of indus trial technology have more up-to-date information, but they are necessarily limited in their scope. Schmittinger recently provided an excellent shorter treatment of the broad field of chlorine technology and applications. After discussing electrolysis and the prin cipal types of cell, this, too, gives rather brief coverage to brine and product processing. It then follows on with descriptions of the major derivatives and direct uses of chlorine and a discussion of environmental issues. The last feature named above has relieved the authors of this work of the obligation to cover applications in any detail. Instead, they provide a concentrated treatment of all aspects of technology and handling directly related to the products of electrolysis. It cov ers the field from a history of the industry, through the fundamentals of thermodynamics and electrochemistry, to the treatment and disposal of the waste products of manufac ture. Membrane cells are considered the state of the art, but the book does not ignore mercury and diaphragm cells. They are considered both from a historical perspective and as examples of current technology that is still evolving and improving. Dear to the heart of a director of Euro Chlor, the book also pays special attention to safe handling of the products, the obligations of Responsible Care®, and process safety management. Other major topics include corrosion, membranes, electrolyzer design, brine pre paration and treatment, and the design and operation of processing facilities. Perhaps uniquely, the book also includes a chapter on plant commissioning. The coverage of membranes is both fundamental and applied. The underlying transport processes and practical experience with existing types of membrane both are covered. The same is true of electrolyzer design. The book explores the basic electrode processes and the funda mentals of current distribution in electrolyzers as well as the characteristics of the leading cell designs. The chapter on brine production and treatment first covers the sources of salt and the techniques used to prepare brine. It then explains the mechanisms by which brine impurities affect cell performance and oudines the processes by which they can be removed or controlled. While pointing out the lack of fundamental science in much of vi FOREWORD the process, it describes the various unit operations phenomenologically and discusses methods for sizing equipment and choosing materials of construction. The chapter on processing and handhng of products is similarly comprehensive. Again, it is good to see that the authors have included a lengthy discussion of safe methods and facilities for the handling of the products, particularly liquid chlorine. While the discussion of the various processing steps includes the topic of process control, there is also a separate chapter on instrumentation which is more hardware oriented. Other chapters deal with utility systems, cell room design and arrangement (with an emphasis on direct current supply), alternative processes for the production of either chlorine or caustic without the other, the production of hypochlorite, industrial hygiene, and speculations on future developments in technology. There is an Appendix with selected physical property data. The authors individually have extensive experience in chlor-alkali technology but with diverse backgrounds and fields of specialization. This allows them to achieve both the breadth and the depth which are offered here. The work is divided into five volumes, successively treating fundamentals, brine preparation and treatment, production technology, support systems such as utilities and instrumentation, and ancillary topics. Anyone with interest in the large field of chlor- alkali manufacture and distribution, and indeed in industrial electrochemistry in general, will find something useful here. The work is recommended to students; chlor-alkali tech nologists; electrochemists; engineers; and producers, shippers, packagers, distributors, and consumers of chlorine, caustic soda, and caustic potash. This book is thoroughly up to date and should become the standard reference in its field. Barrie S. Gilliatt Executive Director Euro Chlor March, 2004 Preface Despite commercial setbacks in recent years, the production of chlorine and alkalis still is of enormous importance, and chlorine and caustic soda both are among the ten largest- volume chemical products in the world. The number of final end uses for the products of a chlor-alkali plant perhaps cannot be matched by any other single plant. There is no comprehensive modern treatment of the chlor-alkali manufacturing process. The authors therefore saw a need for a book on the subject, focusing on chlorine and the alkali products themselves and providing full detail on basic electrochemistry, thermodynamics, and the processing and handling of raw materials and products. Product applications are not covered in any detail. The anticipated audience includes students, electrochemists, all engineers and scientists involved in chlor-alkali technology, and those with a lively interest in an important segment of industry. This work is divided into five volumes. Volume I contains introductory and historical information, followed by the fundamentals of electrochemistry pertinent to chlor-alkali cells. The topics addressed include thermodynamics, kinetics of electrode reactions and electrocatalysis, experimental techniques, energy consumption and its components, and the basic aspects of mercury, diaphragm, and membrane cells. The importance of brine purification, the influence of brine impurities on electrolysis, and the meth ods used for their removal are presented in Volume II. This volume also discusses the three major processes used for electrolysis (diaphragm, mercury, and membrane cells) and offers comparisons of the individual cell technologies employed. Volume III covers the practical aspects of plant engineering and operation. Subject matter includes cell room design and engineering and the processing of chlorine, hydrogen, and caustic soda or potash. There is also an extensive discussion of the safe stor age and handling of the products. Volume IV deals with support systems such as plant utilities and instrumentation hardware and systems. It also contains a chapter dedicated to the commissioning and operation of plants, with an emphasis on mem brane cell rooms. Volume V rounds out the presentation by treating a variety of topics. These include the fundamentals of corrosion; alternative processes for chlorine and caustic, each without the other as co-product; the manufacture of hypochlorites; general safety information (chemical hazards, industrial hygiene, safety programs, waste disposal or minimization); and possible future technological developments in the industry. An Appendix gives some of the physical and chemical properties of relevant materials. Particularly in Volumes II and III, we present examples and discuss specifics of design. These are not to be taken as recommendations for any particular apparatus or viii PREFACE technology. They are offered knowing that many alternatives exist in practice and that some readers may have their own preferred solutions. The authors feel that it is better to provide some practical feel for students and technologists who are unfamiliar with the subject than it is to hesitate because others approaches exist. The authors expect that the typical reader will most frequently consult individual sections of most interest to him or her. Relatively few will read all five volumes consec utively. We have therefore not hesitated to repeat basic information in order to provide quicker understanding of the subject at hand. There are also many cross-references between sections. These will assist the reader seeking broader coverage. The book does not cover first aid or medical practice, nor does it supply complete details on safe handling of materials. Readers must refer to the literature, material safety data sheets, suppliers, and users of the various chemicals and equipment that are dis cussed. While there are summaries of material specifications and suggested analytical schedules, there is likewise not a section on analytical procedures. Safety is of primary importance in manufacture of chemicals. This book therefore makes frequent reference to good practice in design, construction, and operation of chlor- alkali plants. The authors frequently refer to the subject and to various safety codes. We note here that no one code or set of practices may be best in all circumstances, and we take no position in this matter. When specific practices are discussed, it is not to say that they are the best or the only way. Rather, they are offered as possible approaches to specific problems when their inclusion seems to add value to the work. They are not all-inclusive, and as time goes on some will be supplanted by new codes and regulations. Every effort has been made in preparing these volumes to provide information that is accurate and that will be useful to those involved in the chlor-alkali industry. The publisher and the authors jointly and severally make no guarantee and assume no liability in connection with any of the aforesaid information. A NOTE ON USAGE Generally, this book uses metric units, and the authors assume that technologists every where are familiar and comfortable with these units. Strict SI practice is not observed, some published data being kept in units that may be more familiar to those in the chlor-alkali industry. The language and spelling are intended to be standard American, and Amer ican usage (barring the use of metric units) prevails. Thus, an "electrolyser" is an "electrolyzer." ACKNOWLEDGEMENTS The authors wish to acknowledge first the sizable contributions of Thomas A. Weedon, Jr., of Information Technology, Inc., and Dr. Gary M. Shannon, of INEOS Chlor Limited, principal authors, respectively, of Chapters 11 and 13. John M. Lucas made important contributions to the sections on electrical systems. Euro Chlor and The Chlorine Institute generously made many of their publications available to the authors, and both organizations also granted permission to reproduce or PREFACE ix adapt a number of their illustrations. Dr. Barrie S. Gilliatt of Euro Chlor also contributed the Foreword. The authors are grateful to Steve Fitzgerald of Occidental Chemical Cor poration and Dr. Kenzo Yamaguchi of Chlorine Engineers Corporation for providing us with their endorsements of the book. Other contributors of material or technical assistance included: Robert A. Arnold, Jamestown Chemical Steve Brien, Mary Blackburn, Chemical Marketing Associates, Inc Dr. Chao-Peng Chen, Headway Technology - A TDK group company Thomas F. Florkiewicz, Donald J. Groszek, Richard L, Romine and Charles D. Schultz, ELTECH Systems Corporation David Francis, DE NORA ELETTRODI S.p.A., Brent Hardman and members of staff, Powell Fabrication and Manufacturing, Inc. Glenn M. Hymel, Occidental Chemical Corporation Adam Jacobsen, Dorr-Oliver EIMCO Dr. James T. Keating, E.I. duPont de Nemours and Co, Inc. Charles J. Kotzo and Norbert Eckert, Chemetics Library, University of Dortmund Dr. Eric Linak, SRI Consulting Dr. Benno Liike and K. Sambamurty, Uhde GmbH A. Stuart Middleton, Agra Simons C. E. "Skip" Niman, Cargill Salt Company Dr. S. Sarangapani, ICET, Inc. Roger E. Shamel, Consulting Resources Corporation Janet L. White, USFilter Corporation Dr. James R. Wilson, FMC Corporation Dr. Kenzo Yamaguchi, Chlorine Engineers Corporation Reviewers of the material included: Dr. Harry S. Burney Jr., Dow Chemical Corporation Prof. Brian E. Conway, University of Ottawa Dr. Yoshio Harada, Mitsubishi Heavy Industries, Ltd. Glenn M. Hymel, Occidental Chemical Corporation Jeffrey Jones, INEOS Chlor Limited Dr. James T. Keating, Jeffrey L. Jones, Robert D. Theobald, E.I. duPont de Nemours and Co, Inc. Thomas A. Liederbach, Electrode Corporation Thomas J. Navin, Consultant Masao Ohkubo, Sumitomo Chemical Company Dr. Francis Otto, Jr., Alfa Laval Biokinetics Richard L. Romine, Dr. Kenneth L. Hardee, ELTECH Systems Corporation Philip H. Sears, Chlorine Solutions LLC (ex Vulcan Chemical) Dr. Ian F White, Advanced Optimax Consulting, Ltd. Dr. Harry C. Williford, Catalytic, Inc. Dr. Kenzo Yamaguchi, Chlorine Engineers Corporation X PREFACE The authors would Hke to thank Mike Smith for the excellent graphics and his patience in putting up with the constant changes. Finally, Tilak V. Bommaraju would like to acknowledge his wife, Savithri and his daughters, Sudha and Uma for their encouragement during the course of this effort, with special thanks to his daughter, Sudha, for her help in typing from hand written drafts and page-proofing.