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Electrochemical Cell Design PDF

396 Pages·1984·13.475 MB·English
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Electrochemical Cell Design Electrochemical Cell Design Edited by Ralph E. White Department of Chemical Engineering Texas A&M University College Station, Texas PLENUM PRESS • NEW YORK AND LONDON Library of Congress Cataloging in Publication Data Main entry under title: Electrochemical cell design. "Selected contributions from a symposium on recent advances in electrochemi cal cell design, held March 27-31,1983, in Houston, Texas"-T.p. verso. 8ibliography: p. Includes index. 1. Electrolytic cells-Congresses. 2. Electric batteries-Congresses. I. White, Ralph E. QD568.E44 1984 621.31'242 84-11710 ISBN-13: 978-1-4612-9723-9 e-ISBN-13: 978-1-4613-2795-0 001: 10.1007/978-1-4613-2795-0 Selected contributions from a symposium on Recent Advances in Electrochemical Cell Design, held March 27-31, 1983, in Houston, Texas © 1984 Plenum Press, New York Softcover reprint of the hardcover 1s t edition 1984 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013 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, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE This book consists essentially of a collection of papers that were contributed to a national meeting held in Houston, Texas, in 1983. The papers contained herein cover a wide range of electro chemical engineering topics and should serve as useful starting points in the design of electrochemical cells. The editor would like to thank the authors for their contribu tions and patience and the typists, Mrs. Susan 'Firth and Mrs. Jeri Saulsbury, for their efforts. Also, the editor would like to thank Mr. T. Nguyen and Ms. M. A. Nictrolson for their help in preparing the index of this book. R.E. White v CONTENTS Design and Development of Electrochemical Chlor-Alkali Cells • • • • • • • • • 1 S. N. Chatterjee A Simple Model of a Diaphragm - Type Chlorine Cell 25 R. E. White, J. S. Beckerdite, and J. Van Zee Design Principles for Chlorine Membrane Cells 61 K. H. Simmrock Hydroxyl Ion Migration, Chemical Reactions, Water Transport and Other Effects as Optimizing Parameters in Cross-, Co- and Countercurrently Operated Membrane Cells for the Chlor/Alkali Electrolysis .•••••••.•••• 89 K. H. Simmrock Hydraulic Modelling as an Aid to Electrochemical Cell Design. 115 I. Wardle Calculating Mechanical Component Voltage Drops in Electrochemical Cells • • • • 123 I. Wardle Electrolysis Cell Design for Ion Exchange Membrane Chlor-Alkali Process • • • • • • • • • • • • 135 M. Seko, A. Yomiyama, and S. Ogawa Experiences with a Bench-Scale Electrochemical Plant • 161 R. D. Goodin, R. E. W. Jansson, and R. J. Marshall Economic Driving Force in Electro-Organic Synthesis 175 R. E. W. Jansson Design of SU Modularized Electrochemical Cells • 197 A. Bjareklint, L. Carlsson, and B. Sandegren vH viii CONTENTS Electrochemical Techniques for the Extraction of Heavy Metals in Industry: Concepts, Apparatus and Cost • • • • 207 W. Samhaber The Design and Application of Rotating Cylinder Electrode Technology to Continuous Production of Metal • • • • 225 N. A. Gardner and F. C. Walsh Shunt Current Control in Electrochemical Systems - Theoretical Analysis • • • • • • • 259 P. G. Grimes, R. J. Bellows, and M. Zahn Shunt Current Control Methods in Electrochemical Systems - Applications • • • • • • • • • • 277 P. G. Grimes and R. J. Bellows A Simple Model of Exxon's Zn/Br2 Battery. • •••••• 293 J. Van Zee, R. E. White, P. G. Grimes, and R. J. Bellows . . . . . . . A Finite Element Model of Bipolar Plate Cells 311 J. W. Holmes and R. E. White Changes in Overall Ohmic Resistance Due to . . . . . . . . . . Migration/Diffusion of Electrolytes 337 K. H. Lim and E. I. Frances Mathematical Model for Design of Battery Electrodes: Lead-Acid Cell Modelling 357 W. G. Sunu Extension of Newman's Numerical Technique to . . . . . Pentadiagonal Systems of Equations • • • • • • 377 J. Van Zee. G. Kleine. R. E. White, and J. Newman Index 391 DESIGN AND DEVELOPMENT OF ELECTROCHEMICAL CHLOR-ALKALI CELLS S. N. Chatterjee Durgapur Chemicals Ltd. Calcutta, India ABSTRACT The gradual development of electrochemical chlor-alkali processes is described. The processes described are as follows: diaphragm, mercury and membrane. These processes are compared and various design and selection factors are given for a variety of membrane processes. INTRODUCTION The manufacture of chlor-alkali by an electrochemical process is an old industry. The first diaphragm process was commissioned in 1886 and has undergone a slow evolution since then. Cell amperage has increased gradually with time from 1 KA to 100 KA. The main drawback of the diaphragm cells of early days was a large anode/cathode gap to accomodate diaphragm swelling resulting in high energy consumption, low concentration of caustic soda, and high chloride impurity in the caustic soda, which made it unsuitable for some industries like production of Rayon, etc. This necessitated the development of the mercury cell process. The technology of mercury cells even up to the mid-fifties was not very advanced when compared to that of the eighties. With improved cell design, energy consumption and other 2 S.N.CHATTERJEE operating costs have been brought down considerably. The technology of both cells was improved further by the use of dimensionally stable metallic anodes in 1968. Due to a large increase in oil prices between 1973 and 1980 and stringent effluent regulations, a new chlor-alkali technology was needed. As a result of research and development in pilot plant studies throughout the world, the first chlor-alkali membrane cell was commissioned in 1975. There is presently a continuous effort from every corner to further bring down energy consumption, capital cost, and operating cost in commercial membrane cells. DC energy consump tion of 4000 kWh/ton in the mid-fifties, for instance, was brought down to 2200 kWh/ton in 1983. Diaphragm Cells Up to the early seventies all diaphragm-type electrolyzers were equipped with graphite anodes and asbestos diaphragms. In the course of time the design became even more sophisticated. The bottom was ~f complicated form. A 10 - 12mm electrode gap was kept to accomodate diaphragm swelling. The maximum specific load was around 1.5 KA/m2• The compact and nearly cubic form of the electrolyzer, which resulted in high current density in the steel cathode, had to be reinforced by copper bus bars in order to reduce the thermal load and energy losses. The introduction of metal anodes with improved diaphragms removed these limitations resulting in reduction of the electrode gap to 3 - 4mm. A smaller electrode has necessitated closer fabrication tolerances for the anode. One of the improved diaphragm cell designs is the UHDE HU type cell design. This (see Table 1) is based on the idea of keeping the cell rows and the current and product paths short in order to reduce DESIGN OF CHlOR-AlKALI CEllS 3 Table 1. u Electrolyzer Anode Diaphragm (V) General Graphite Asbestos 0.9 - 1.0 4.4 - 4.6 General Metal Asbestos 0.5 - 0.6 3.6 - 3.8 Hooker H4 Metal HAPP 0.40 3.38 UHDE HU Metal HAPP 0.36 3.30 * Cell electrical resistance factor in the equation U 2.36 + KI with I in KA. Table 2. Cell Characteristics: Kuhera SK 330 Cell Current density, amp/sq m 2,340 Cell voltage 3.3 Current efficiency, % 96.5 DC kWh/metric ton, NaOH 2,292 Diaphragm life, days 200 to 400 Catholyte conc., % NaOH 11 - 12 NaCI02 in catholyte, % 0.002 - 0.01 the conductor and piping requirements and to save space. Also the by-pass switch for this cell system is in an advantageous position below the row of cells. In addition, a polymer modified asbestos dia phragm (HAPP) developed by Hooker is used in the HU type electro lyzers. This diaphragm is dimensionally stable, and its high mechanical stability increases its service life from 200 to 500 days depending on the brine purity. The low K value of 0.36 in Table 1 for the HU type electrolyzer has not been surpassed apparently by any other diaphragm electrolyzer using the same anodes and diaphragms. Improved diaphragms offer several other advantages such as: (a) less resistance to cell room upsets; (b) lower hydrogen in chlorine gas; (c) ease of recovering spent diaphragm material; (d) better reproduci bility of cell performance throughout the operating period; (e) longer diaphragm life during storage; and (f) twice the diaphragm life compared to standard asbestos. Kuhera Chemical Industry has developed a cell which uses a molded asbestos diaphragm and operates at 330 KA (see Table 2 for performance). 4 S. N. CHATTERJEE Some of the additional developmental work taking place for further improvement in diaphragm cell technology is: (a) catalytic coating of cathodes to reduce hydrogen over voltage; (b) microporous diaphragms which have the possibility of the elimination of asbestos, improved current efficiency and higher caustic strength; and (c) dynamic gel diaphragm having the potential of ion exchange functions in a diaphragm cell at much lower cost than mem brane cells. Mercury Cell For the last 25 years there has been rapid growth in electrochem ical chlor-alkali technology. This has been achieved by improving the design concept to optimize industrial production techniques superceding the technology up to the 1950's. For our discussion in this paper we shall consider mercury cells up to the fifties as older cells. Reduction of investment cost became necessary in the following areas: (a) cells; (b) mercury inventory; (c) graphite requirement; (d) bus bar requirement; and (e) civil work. Attention was also di verted to reduction of operating cost by lower graphite and mercury consumption, lower bus bar loss and less down time of the plants. Design in the follOwing areas was significantly improved: (a) Current Density and Mercury Inventory - The arrangement of cathodic discs in older cells was replaced by bare bottom cells. This altered design concept necessitated higher current density and a higher slope of the cell from 0.5% to even 1.5%. These changes resulted in reduction of energy consumption and mercury inventory. Mercury inventory, cathode surface area and cell house area per ton of caustic

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