Sulphonation Technology in the Detergent Industry Sulphonation Technology • In the Detergent Industry by W. Herman de Groot Springer-Science+Business Media, B.V. Library of Congress Cataloging-in-Publication Data Herman de Groot. W. Sulphonation technology in the detergent industry I by W. Herman de Groot. p. cm. Inc 1 udes index. ISBN 978-90-481-4088-6 ISBN 978-94-015-7918-6 (eBook) DOI 10.1007/978-94-015-7918-6 1. Detergents. Synthetic. 2. Sulphonation. 1. Title. TP990.G68 1991 668' .14--dc20 91-2592 ISBN 978-90-481-4088-6 Disclaimer. While every effort has been made to ensure the accuracy of the information given in this publication, neither the Author nor the Publisher can in any way accept responsibility for damages or liabilities of any kind which may be claimed to result from the use of this book. Printed on acid-free paper AII Rights Reserved © 1991 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1991 Softcover reprint ofthe hardcover Ist edition 1991 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, inc\uding photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner. DEDICATION This book is dedicated to friends with whom I have worked or still work in the sulphonation field. They live throughout the world and work for a variety of companies. I name them in alphabetical order: Jorge Aparicio Klaas Maat Mario Ballestra Miel Marchand Jim Begnel Hans Mik Stefano Cardone Franco Moretti Charley Carroll Gianmaria Moroni Dimitri Corso Franco Olivieri Birger Dahl Sid Palmer John Davidson Roman Pardon Joao Ferreira da Fonseca Neto Alfredo Parodi Norman Forster Luigi Perani Marco Galateri di Genola Roy Regan Manfred Gehrmann Sylvere van Renterghem Dave Hill Manfred Schwartz Frans van der Hoeven lnarto Setiadi Ray Hurd Bob Sharod Simon Kellet Luciano Spadon Bernard Lemaire S.K. Subbaroyan Giorgio Locatelli Romeo del Vecchio Mike de Lucia Antonio Zalaquett and others too numerous to mention, my heartfelt thanks. Wim vii PREFACE This book is about Sulph(on)ation Technology in its technical entirety, aiming at superiority in final product quality, raw material utilisation, sustained plant reliability and safety, minimisation of liquid effluent and gaseous emissions; it is about the total quality of the operation. It will be of value to engineers and chemists who are, or will be, involved in the practical daily operation of sulphonation plants or R&D activities. The book can also be used as a tool for the teacher in preparing fmal year projects in a chemical engineering curriculum. The book covers sulphonation of alkylbenzenes, primary alcohols, alcohol ethers, alpha-olefIns and fatty acid methyl esters, with a strong emphasis on the sulphur-based S~/air sulphonation technology. The first part deals with raw material specifications, hazards, storage, handling and physical properties. In the following section the process chemistry is discussed, indicating main chemical reactions, undesired parallel and consecutive reactions, exothermal heat effects and all other process chemistry data that are relevant for process selection and equipment design. The section about the actual process equipment from the various plant equipment suppliers (Ballestra, Chemithon, Mazzoni, Meccaniche Modeme and Lion Corp.) takes into account the chemical reaction engineering aspects derived from the sulphonation technology processing chemistry. Product quality, product storage and handling, product safety and physical properties are the contents of the next section. The effluent handling and exhaust gas treatment of the SOiair sulphonation technology are further discussed in detail. Plant instrumentation and computer control in various degrees of sophistication are described in the next section. Plant housing, space requirements, lay-out and required plant documentation are briefly discussed. A further chapter of the book describes the 20% oleum and sulphuric acid based sulphonation technology. This part is less extensive, since the S~/air process is becoming predominant in the manufacture of detergent actives, taking over from the older oleum and sulphuric acid technol ogies. A final chapter outlines the virtues of the sulphonation technology as a "learning paradise" for chemical engineers. All kinds of problems and disciplines come together in one concise operation: highly exothermic reactions in combination with substantial viscosity increase of the reaction products, undesired parallel and consecutive reactions affecting final product quality, environmental problems, hazardous and corrosive chemicals demanding careful selection of plant equipment, design and construction materials. TABLE OF CONTENTS Preface vii Acknowledgements xv About the author xvii List of figures xix List of tables xx List of process and instrumentation diagrams (Ballestra) xxi 1. Application of sulphonates as anionic surfactants in household products 1 1.1. Introduction 1 1.2. Most important sulph(on)ates 1 1.3. Bibliography 4 2. A brief description of the sulphonation processes used for the manufacture of active detergents 5 2.1. Introduction 5 2.2. Sulphur-based S03/air sulphonation 7 2.3. Sulphonation with 20% oleum 10 2.4. Sulphonation with sulphuric acid 11 2.5. Sulph(on)ation with chlorosulphonic acid 11 2.6. Bibliography 12 3. Raw materials quality, storage, handling and safety 13 3.1. Sulphur 13 3.1.1. Sulphur quality 13 3.1.2. Sulphur storage, handling and safety 14 3.1.3. Sulphur hazard data 16 3.1.4. Engineering data-physical property data sheet 18 3.2. Sulphur dioxide 19 3.2.1. Hazard data 19 3.2.2. Engineering data-physical property data sheet 20 3.3. Sulphur trioxide 21 3.3.1. Hazards of sulphur trioxide 21 3.3.2. Liquid S03 (sulphan) storage and handling 24 3.3.3. Engineering data-physical property data sheet 25 3.4. 65% oleum and 20% oleum 25 3.4.1. Hazards of oleum 65 and oleum 20 25 3.4.2. Oleum storage and handling 27 3.4.3. Engineering data-physical property data sheet 27 3.5. Sulphuric acid and 'spend acids' 28 3.5.1. Hazards of sulphuric acid 28 3.5.2. Storage and handling 30 3.5.3. Engineering data-physical property data sheet 31 3.6. Alkylbenzenes 32 3.6.1. Alkylbenzenes: quality 32 3.6.2. Alkylbenzenes: safety information 34 3.6.3. Alkylbenzenes: storage and handling 34 3.6.4. Engineering data-physical property data sheet 36 3.7. Primary alcohols 37 x 3.7.1. Primary alcohols: quality 37 3.7.2. Primary alcohols: safety information 39 3.7.3. Primary alcohols: storage and handling 39 3.7.4. Engineering data-physical property data sheet 40 3.8. Primary alcohol ethoxy lates 41 3.8.1. Primary alcohol ethoxylate quality 41 3.8.2. Primary alcohol ethoxylates: safety information 43 3.8.3. Primary alcohol ethoxylates: storage and handling 43 3.8.4. Engineering data-physical property data sheet 44 3.9. Alpha-olefins 44 3.9.1. Alpha-olefins: quality 45 3.9.2. Alpha-olefins: safety information 46 3.9.3. Alpha-olefins: storage and handling 47 3.9.4. Engineering data-physical property data sheet 47 3.10. Fatty acid methyl esters (FAME) 48 3.10.1. FAME quality 48 3.10.2. FAME: storage and handling 49 3.10.3. Engineering data-physical property data sheet 50 3.11. Sodium hydroxide (caustic soda) and sodium hydroxide solution (45-50%)(caustic soda liquor) 50 3.11.1. Sodium hydroxide quality 51 3.11.2. Sodium hydroxide safety information 51 3.11.3. Storage and handling 54 3.11.4. Engineering data-physical property data sheet 55 3.12. Sodium carbonate (soda ash) 57 3.12.1. Sodium carbonate quality 57 3.12.2. Safety information 57 3.12.3. Storage and handling 59 3.12.4. Engineering data-physical property data sheet 59 3.13. Ammonium hydroxide (ammonia liquor) 61 3.13.1. Ammonium hydroxide quality (NHOH) 61 4 3.13.2. Safety information 61 3.13.3. Storage and handling 63 3.13.4. Engineering data-physical property data sheet 64 3.14. Chlorine (CI2) 64 3.14.1. Chlorine quality 65 3.14.2. Chlorine safety information 65 3.14.3. Storage and handling 67 3.14.4. Engineering data-physical property data sheet 68 3.15. Sodium hypochlorite 68 3.15.1. Sodium hypochlorite quality 69 3.15.2. Hypochlorite safety information 69 3.15.3. Storage and handling of NaOCl solutions 71 3.15.4. Engineering data-physical property data sheet 73 3.16. Hydrogen peroxide 73 3.16.1. Hydrogen peroxide quality 73 3.16.2. Hydrogen peroxide safety information 73 3.16.3. Storage and handling 75 xi 3.16.4. Engineering data-physical property data sheet 75 3.17. Ethyl alcohol (Ethanol) 76 3.17.1. Ethyl alcohol quality 76 3.17.2. Ethyl alcohol safety information 76 3.17.3. Storage and handling 78 3.17.4. Engineering data-physical property data sheet 78 3.18. Bibliography 79 4. Process chemistry and principles 83 4.1. S03/air production chemistry 83 4.1.1. Sulphur combustion with excess dry air to S02f'air" 83 4.1.2. Conversion of S02 to S03 85 4.2. Sulphonation chemistry 87 4.2.1. Alkylbenzene sulphonation 87 4.2.2. Primary alcohol sulphation 90 4.2.3. Ethoxylated alcohol sulphation 92 4.2.4. Alpha-olefm sulphonation (AOS) 95 4.2.5. Fatty acid methyl ester (FAME) sulphonation 97 4.2.6. Summary sulphonation reaction process chemistry 99 4.3. Neutralisation chemistry 100 4.3.1. Introduction 100 4.3.2. Alkylbenzene sulphonic acid (LABSA) neutralisation 101 4.3.3. Alkyl hydrogen sulphate (ROS03H) and alkyl ether hydrogen sulphate R(OC~CH2).oS03H neutralisa- tion 104 4.3.4. Neutralisation/hydrolysis of alkene sulphonic acid and sultones 105 4.3.5. Alpha sulphonated fatty acid methylester sulphonic acid neutralisation and bleaching 106 4.4. Bleaching chemistry 107 4.5. Exhaust gas treatment chemistry 109 4.6. Bibliography 110 5. Processing equipment 112 5.1. Introduction 112 5.2. S03/air generation 112 5.2.1. Sulphur melting and refining 112 5.2.2. Air drying equipment 115 5.2.3. Sulphur burners 119 5.2.4. S02/air coolers and hotgas filters 120 5.2.5. S02 -S03 converter tower 121 5.2.6. S03 absorbers 124 5.2.7. S03/air coolers -oleum collection and mist filtration 125 5.2.8. S03/air gas splitting 125 5.2.9. Conclusions 126 5.3. S03 generation from liquid S03 127 5.4. S03 generation from 65% oleum 129 5.5. Sulph(on)ation reactor systems 129 xii 5.5.1. General chemical reaction engineering aspects related to sulphonation reactor systems 129 5.5.2. The Ballestra Sulphurex crSR system 132 5.5.3. Chemical reaction engineering aspects related to sulph(o n)ation in falling-film reactor 134 5.5.4. The Ballestra Sulphurex F system (multi-tube falling- film reactor MTFFR) 142 5.5.5. The Mazzoni Sulpho film reactor (multi-tube falling- film reactor) 145 5.5.6. The Meccaniche Moderne falling-film reactor 146 5.5.7. The Chemithon falling-film reactor 148 5.5.8. The Chemithon jet impact reactor 150 5.5.9. The T-O sulphonation reactor system 151 5.5.10. Ageing (digesting) and hydrolysing (stabilising) equipment for alkylbenzene sulphonic acid 153 5.5.11. Desired criteria for sulphonation reactor design versus sulphonation reactor systems from suppliers 155 5.5.12. Conclusions: sulphonation reactor systems 157 5.6. Neutralisation equipment 157 5.6.1. Chemical engineering aspects related to neutralisation reactor systems 157 5.6.2. The Ballestra stirred-tank neutraliser system 160 5.6.3. Ballestra double-step neutralisation system (Neutrex) 161 5.6.4. The neutralisation equipment of Meccaniche Moderne, Mazzoni and Chemithon 162 5.7. Chlorine dosing equipment for in-situ manufacture of diluted NaOCI solutions 165 5.8. Sultone hydrolysis equipment 166 5.9. Exhaust gas cleaning equipment 167 5.9.1. The electrostatic precipitator (ESP) 167 5.9.2. S02 removal from exhaust gas, the caustic scrubber and sulphite oxidation 175 5.9.3. Exhaust gas stack and composition of exhaust gas leaving the stack 179 5.10. Bibliography 179 6. Product quality, storage, handling and safety 181 6.1. Equipment suppliers guaranteed final product specification 181 6.2. In-plant analytical methods to check product quality 190 6.3. Linear alkylbenzene sulphonic acid (LABSA) quality, storage, handling and safety 191 6.3.1. LABSA quality 191 6.3.2. LABSA safety information 191 6.3.3. Storage and handling 191 6.3.4. Engineering data-physical property data sheet 192 6.4. Linear alkylbenzene sulphonate paste (LABS) quality, storage, handling and safety 193 6.4.1. LAB sulphonate paste quality 193 xiii 6.4.2. LAB sulphonate safety information 193 6.4.3. Storage and handling 193 6.4.4. Engineering data-physical property data sheet 194 6.5. Primary alcohol sulphates (PAS) 195 6.5.1. Primary alcohol sulphate quality 195 6.5.2. Primary alcohol sulphate safety information 195 6.5.3. Storage and handling of PAS 195 6.5.4. Engineering data-physical property data sheet 196 6.6. Primary alcohol ethoxysulphates, lauryl ether sulphates (LES) quality, storage, handling and safety 197 6.6.1. Factors which affect the quality 197 6.6.2. Alcohol ether sulphate safety information 200 6.6.3. Microbiological control of dilute alcohol ether sulphates (and alcohol sulphates, 27% AM) 200 6.6.4. High-active alcohol ether sulphates (approx. 60 to 70% AD) handling and storage 200 6.6.5. Engineering data-physical property data sheet 203 6.7. Alpha-olefin sulphonates (AOS) quality 204 6.8. Fatty acid methyl ester sulphonates quality 205 6.9. Bibliography 205 7. Exhaust gas and effluent treatment S03/air sulphonation plants 207 7.1. Introduction 207 7.2. Treatment of the exhaust gas 207 7.2.1. Removal of residual S02 in exhaust gas leaving sulphonation system 207 7.2.2. Sulphuric acid mist removal from exhaust gas 207 7.2.3. Organic mist removal from exhaust gas 208 7.2.4. Chemical analysis of exhaust gas leaving the sulphona- tion plant stack 208 7.2.5. Summary table of various levels of gaseous effluents 209 7.3. Treatment of liquid effluents 209 7.3.1. Treatment of collected oleum from S03 coolers, demisters and cyclones 209 7.3.2. Treatment of ESP residues 210 7.3.3. Diluted caustic effluent disposal ex S02 scrubber 210 7.3.4. Summary table of various quantities of liquid ef- fluents 211 7.4. Bibliography 211 8. Plant start-up/shut-down and operational conditions sulphonation/neutrali- sation 212 8.1. Plant start-up 212 8.2. Plant shut-down 213 8.3. Operating conditions 213 8.3.1. Sulph( on)ation 213 8.3.2. Neutralisation 214 8.4. Bibliography 215