Sulfuric Acid Manufacture Intentionally left as blank Sulfuric Acid Manufacture Analysis, Control, and Optimization By Matthew J King Perth, Western Australia William G Davenport Tucson, Arizona Michael S Moats Rolla, Missouri AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Elsevier 30 Corporate Drive, Suite 400, Burlington, MA 01803, USA 525 B Street, Suite 1800, San Diego, CA 92101-4495, USA Second edition © 2013, 2006 Elsevier Ltd All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (þ44) (0) 1865 843830; fax (þ44) (0) 1865 853333; email: permissions@elsevier.com Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress For information on all Elsevier publications visit our web site at store.elsevier.com Printed and bound in Poland 13 14 15 16 17 10 ISBN: 978-0-08-098220-5 Contents Preface xv Overview 1.1 Catalytic oxidation of SO2 to SO3 1.2 H2SO4 production 1.3 Industrial flowsheet 1.4 Sulfur burning 1.5 Metallurgical offgas 1.6 Spent acid regeneration 1.7 Sulfuric acid product 1.8 Recent developments 1.9 Alternative processes 1.10 Summary Production and consumption 2.1 Uses 2.2 Acid plant locations 2.3 Price 2.4 Summary 11 13 14 14 16 Sulfur 3.1 3.2 3.3 3.4 3.5 3.6 3.7 19 20 20 21 22 23 28 29 Metallurgical offgas cooling and cleaning 4.1 Initial and final SO2 concentrations 4.2 Initial and final dust concentrations 4.3 Offgas cooling and heat recovery 4.4 Electrostatic collection of dust 4.5 Water scrubbing 4.6 H2O(g) removal from scrubber exit gas 4.7 Summary burning Objectives Sulfur Molten sulfur delivery Sulfur atomizers and sulfur burning furnaces Product gas Heat recovery boiler Summary 1 4 6 7 31 31 33 34 35 37 43 44 vi Contents Regeneration of spent sulfuric acid 5.1 Spent acid compositions 5.2 Spent acid handling 5.3 Decomposition 5.4 Decomposition furnace product 5.5 Optimum decomposition furnace operating conditions 5.6 Preparation of offgas for SO2 oxidation and H2SO4 making 5.7 Summary 47 47 51 51 52 53 54 56 Dehydrating air and gases with strong sulfuric acid 6.1 Chapter objectives 6.2 Dehydration with strong sulfuric acid 6.3 Dehydration reaction mechanism 6.4 Residence times 6.5 Recent advances 6.6 Summary 59 59 61 64 65 70 70 Catalytic oxidation of SO2 to SO3 7.1 Objectives 7.2 Industrial SO2 oxidation 7.3 Catalyst necessity 7.4 SO2 oxidation “heatup” path 7.5 Industrial multicatalyst bed SO2 oxidation 7.6 Industrial operation 7.7 Recent advances 7.8 Summary 73 73 73 75 84 84 87 89 89 SO2 oxidation catalyst and catalyst beds 8.1 Catalytic reactions 8.2 Maximum and minimum catalyst operating temperatures 8.3 Composition and manufacture 8.4 Choice of size and shape 8.5 Catalyst bed thickness and diameter 8.6 Gas residence times 8.7 Catalyst bed temperatures 8.8 Catalyst bed maintenance 8.9 Summary 91 91 95 95 96 97 98 99 100 100 Production of H2SO4(ℓ) from SO3(g) 9.1 Objectives 9.2 Sulfuric acid rather than water 9.3 Absorption reaction mechanism 9.4 Industrial H2SO4 making 9.5 Choice of input and output acid compositions 9.6 Acid temperature 103 103 104 105 107 115 116 Contents 9.7 9.8 9.9 9.10 9.11 vii Gas temperatures Operation and control Double contact H2SO4 making Intermediate versus final H2SO4 making Summary 116 116 118 120 120 Break 123 10 Oxidation of SO2 to SO3—Equilibrium curves 10.1 Catalytic oxidation 10.2 Equilibrium equation 10.3 KE as a function of temperature 10.4 KE in terms of % SO2 oxidized 10.5 Equilibrium % SO2 oxidized as a function of temperature 10.6 Discussion 10.7 Summary 10.8 Problems 125 125 127 128 129 129 132 132 132 11 SO2 oxidation heatup paths 11.1 Heatup paths 11.2 Objectives 11.3 Preparing a heatup path—The first point 11.4 Assumptions 11.5 A specific example 11.6 Calculation strategy 11.7 Input SO2, O2, and N2 quantities 11.8 Sulfur, oxygen, and nitrogen molar balances 11.9 Enthalpy balance 11.10 Calculating level L quantities 11.11 Matrix calculation 11.12 Preparing a heatup path 11.13 Feed gas SO2 strength effect 11.14 Feed gas temperature effect 11.15 Significance of heatup path position and slope 11.16 Summary 11.17 Problems 135 135 135 136 136 136 137 138 139 140 142 143 143 145 147 148 149 150 12 Maximum SO2 oxidation: Heatup path-equilibrium curve intercepts 12.1 Initial specifications 12.2 % SO2 oxidized-temperature points near an intercept 12.3 Discussion 12.4 Effect of feed gas temperature on intercept 12.5 Inadequate % SO2 oxidized in first catalyst bed 12.6 Effect of feed gas SO2 strength on intercept 12.7 Minor influence—Equilibrium gas pressure 151 151 151 153 153 154 154 154 viii Contents 12.8 12.9 12.10 12.11 12.12 12.13 12.14 Minor influence—O2 strength in feed gas Minor influence—CO2 in feed gas Catalyst degradation, SO2 strength, and feed gas temperature Maximum feed gas SO2 strength Exit gas compositionintercept gas composition Summary Problems 155 155 157 158 159 160 160 13 Cooling first catalyst bed exit gas 13.1 First catalyst bed summary 13.2 Cooldown path 13.3 Gas composition below equilibrium curve 13.4 Summary 13.5 Problem 161 161 161 164 164 164 14 Second 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 14.10 14.11 14.12 14.13 catalyst bed heatup path Objectives % SO2 oxidized redefined Second catalyst bed heatup path A specific heatup path question Second catalyst bed input gas quantities S, O, and N molar balances Enthalpy balance Calculating 760 K (level L) quantities Matrix calculation and result Preparing a heatup path Discussion Summary Problem 167 167 167 168 170 170 171 171 172 173 173 173 175 176 15 Maximum SO2 oxidation in a second catalyst bed 15.1 Second catalyst bed equilibrium curve equation 15.2 Second catalyst bed intercept calculation 15.3 Two bed SO2 oxidation efficiency 15.4 Summary 15.5 Problems 177 177 178 180 181 181 16 Third catalyst bed SO2 oxidation 16.1 2-3 Cooldown path 16.2 Heatup path 16.3 Heatup path-equilibrium curve intercept 16.4 Graphical representation 16.5 Summary 16.6 Problems 183 183 184 187 187 187 187 Contents ix 17 SO3 and CO2 in feed gas 17.1 SO3 17.2 SO3 effects 17.3 CO2 17.4 CO2 effects 17.5 Summary 17.6 Problems 189 189 193 193 197 197 198 18 Three 18.1 18.2 18.3 18.4 18.5 18.6 18.7 18.8 18.9 18.10 18.11 18.12 18.13 199 199 199 199 201 202 202 204 204 206 206 207 208 209 19 After-H2SO4-making SO2 oxidation 19.1 Double contact advantage 19.2 Objectives 19.3 After-H2SO4-making calculations 19.4 Equilibrium curve calculation 19.5 Heatup path calculation 19.6 Heatup path-equilibrium curve intercept calculation 19.7 Overall SO2 oxidation efficiency 19.8 Double/single contact comparison 19.9 Summary 19.10 Problems 211 211 213 213 215 216 216 217 221 222 227 20 Optimum double contact acidmaking 20.1 Total % SO2 oxidized after all catalyst beds 20.2 Four catalyst beds 20.3 Improved efficiency with five catalyst beds 20.4 Input gas temperature effect 20.5 Best bed for Cs catalyst 20.6 Triple contact acid plant 20.7 Summary 229 230 230 231 231 232 233 234 21 Enthalpies and enthalpy transfers 21.1 Input and output gas enthalpies 21.2 H2SO4 making input gas enthalpy 235 235 238 catalyst bed acid plant Calculation specifications Example calculation Calculation results Three catalyst bed graphs Minor effect—SO3 in feed gas Minor effect—CO2 in feed gas Minor effect—Bed pressure Minor effect—SO2 strength in feed gas Minor effect—O2 strength in feed gas Summary of minor effects Major effect—Catalyst bed input gas temperatures Discussion of book’s assumptions Summary Index mist precipitation, 33 precipitator plants, 38t, 39t removal, 33 scrubbing, 33, 36 Dust removal, spent sulfuric acid, 54 E E’ volume, 215–216 Economizers, bypassing, 244f 460 K, 247–248 470K, 247–248 480K, 247–248 Electrodes, 35 Electrostatic precipitators dry, 37f dust collection, 35–36 schematic, 36f wire, 37f Elemental sulfur atomizers, 22–23 delivery, 21–22 furnaces, 22–23 H2SO4 production, melting point, 20 pipes for, 21–22 pumps for, 21–22 viscosity, 20–21, 21f Enthalpies, gas bypassing with economizers, 246 first catalyst bed, 238 H2SO4 making, 238–239 heat transfers, 240t N2, 238 O2, 238 SO2, 238 SO3, 238 temperatures, 240t H2SO4 making balances, 269–270 heat transfers, 236f, 239 between catalyst beds, 240 rates, 240–241 third catalyst bed, 239–240 input gas, 235–238 output gas, 235–238 second catalyst bed, 238 third catalyst bed, 237t heat transfers, 239–240 Enthalpy balances CO2 feed gases, 195 497 heatup paths cell equations, 145 N2 gas, 142t numerical, 141–142 O2 gas, 142t SO2 gas, 140–142, 142t SO3 gas, 142t second catalyst bed, 171–172, 172t heatup path, 169 Environmental emissions, WSA process, 300f Equilibrium after-H2SO4-making, curve calculations, 215–216, 219f, 220f catalyst beds, 33 e’ volume, 215–216 f’ volume, 215–216 heatup path, 216–217 preparation, 216 %SO2 oxidation definitions, 216 temperature points, 219t first catalyst bed, 162f gas composition, 164 gas recycling, 317 H2O gas pressures, 63t heatup path intercepts, 155f acid regeneration, 156 catalyst beds, 153, 159, 159f catalyst degradation, 157 catalyst layers, 157 CO2 strength, 155–157, 157f exit gas composition, 159 feed gas, 151, 158f feed gas temperature, 153, 154f, 157 gas pressure, 154–155, 156f initial specifications, 151 O2 strength, 155, 156f plots, 153f second catalyst bed, 170 %SO2 oxidized-temperature points, 151–152, 152t SO2 strength, 157, 158–159, 158f second catalyst bed, 170 SO2 oxidation, 177–178 SO2 catalytic oxidation to SO3, 83f, 125–127 definition, 126–127 equation for, 127–128 feed gas percentages, 127f, 131, 131f gas balances, 132 498 Equilibrium (Continued) heatup paths, 149f Ke function, temperature effects, 128, 129 N2 feed gas, 126f O2 feed gas, 126f, 130, 131f pressure effects, 130, 130f second catalyst bed, 177–178 temperature effects, 129–131 third catalyst bed, 187 SO2 gas catalytic oxidation to SO3, 83f, 125–127 curves, 149f heatup path intercepts, 157, 158–159, 158f SO3 gas curve equation, in feed gases, 189–190, 193 feed gases, 189–190, 193 sulfur emissions, 342–343 WSA process, 288f Exothermic reactions acid temperature control, 267 H2SO4 production, from SO3 gas, 104 F F’ volume, 215–216 Feed gases CO2, 193–196 carbon balance equation, 194 catalyst bed comparisons, 193t enthalpy balance equation, 195 first catalyst bed, 196t, 197f heatup paths, 193, 194–196, 197 nitrogen input quantity, 195 oxygen balance equation, 194 equilibrium-curve intercepts, 151, 158f gas temperature, 153, 154f, 157 gas recycling, 317f SO2 catalytic oxidation to SO3, 74, 76t, 190 equilibrium, 127f, 131, 131f feed gas, 190 first catalyst bed, 161, 204–206, 204f, 205f heatup paths, 136, 145–148 second catalyst bed, 204–206, 204f, 205f third catalyst bed, 204–206, 204f, 205f SO2 heatup paths, 136 Index SO3, 189–193 changed balances, 191–192 enthalpy balances, 191 equilibrium curve equation, 189–190, 193 first catalyst bed, 202 heatup path matrix, 190, 192t second catalyst bed, 202 SO2 input equation, 190 third catalyst bed, 202 sulfur emissions, 345–346 WSA process concentrations, 297 H2SO4 production, 285 SO2 oxidation, 298f Feed gas dilution with air, 321–322, 322t Fertilizer production, Fifth catalyst bed, after-H2SO4-making, 231 SO2 oxidation, 231f First catalyst bed bed pressure, 204 calculations input points, 201f intercept points, 201f, 203f, 203t results, 199–200 specifications, 199, 200t CO2 feed gases, 196t, 197f, 202–203 equilibrium curve, 162f gas composition, 164 gas enthalpies, 238 gas recycling, 314f, 315f, 316f, 318f graphs, 201–202 heatup paths, 202 SO2 oxidation efficiency, 202 H2SO4 production, 258, 260–261 heat loss assumptions, 208–209, 209f heatup path, 162f graphs, 202, 203f industrial gas cooling, 163–164 input gas, 207f temperatures, 207 intercept point, 162f attainment assumption, 209 calculations, 201f, 203f, 203t O2 in feed gas, 206 volume effects, 206f schematic, 162f Index SO2 catalytic reactions, 97f, 99f in feed gas, 204–206, 204f, 205f production process, 207 SO2 oxidation catalytic reactions, 97f, 99f cooldown path, 161–164, 163f feed gas, 161 graph efficiency, 202 inefficiencies, 161 values, 208f SO3 in feed gas, 202 steady-state assumptions, 208 FLEXERAMIC packing, 70f Flow rates, acid temperature control, 280 Flowsheets H2SO4 after-H2SO4-making, 214f production, 4, 5f single contact production, 252f from SO3 gas, 104f metallurgical offgas, 32f offgas, 32f spent acid regeneration, 48f spent sulfuric acid, 48f sulfur burning, 20f WSA process, 285–287, 286f Flue gas concentration, 302 Fluorine removal, offgas scrubbing, 43 460 K economizers, 247–248 470K economizers, 247–248 480K economizers, 247–248 Fourth catalyst bed, after-H2SO4-making, 230 SO2 oxidation, 230f Furnaces decomposition, for spent sulfuric acid, 49f, 51–52 O2 content effects, 54 operations, 50t, 53–54, 53f products, 52 temperature effects, 53 elemental sulfur, 22–23 H2SO4 production, ceramic retorts, 11 sulfur burning, 19f, 22–23, 23f, 25t G Gas cleaning plants, metallurgical offgas, 40t Gas cooling See Industrial gas cooling Gas dehydration See Dehydration, gas 499 Gas enthalpies See Enthalpies, gas Gas flues, bypassing, 244f Gas recycling acid plant performance, 318 alternatives, 321–322 appraisal, 319 BAYQIK process, 322 calculations, 313–314 catalyst bed comparisons, 321, 321f effect of extent, 314–315 equilibrium, 317 equipment requirements, 319 feed gas, 317f feed gas dilution with air, 321–322, 322t first catalyst bed, 314f, 315f, 316f, 318f industrial SO3 applications, 319–321 LUREC process, 319–320, 320t objective, 313 oxidation rates, 315 preconverters, 322, 323f SO2, 317 temperature effects, 315–317, 316f calculation methods, 316f third catalyst bed, 320f Gas velocity, WSA process, 309, 309t Gas-dehydration flows, H2SO4 production, Gold, H2SO4 production, 11 H H2O (gas) equilibrium pressures, 63t feed rate variations, 63 after gas hydration, 61 before gas hydration, 61 H2SO4 production inputs, 253–254 offgas scrubbing, 43–44, 44f spent sulfuric acid, 47 H2O (liquid) acid temperature control, steam injection requirements, 279 condensers, in WSA process, 307–308 H2SO4 production requirements, 259, 259f from SO3 gas, 104 H2SO4 See also After-H2SO4-making; Afterintermediate-H2SO4-making; Decomposition furnaces acid plant locations, 14 acid temperature control 500 H2SO4 (Continued) calorimetric measurements, 268 enthalpy of mixing, 268–269 final equations, 271–272 inputs, 269t mixing heat, 269 outputs, 269t, 270, 271 consumption, 13–14 fertilizer production, phosphate reactions, 13 world demographics, 13t dehydration, 60f acid strength, 62–64 circuits, 62f conductivity cells, 64 industrial method, 61–64 elemental sulfur, enthalpies, 238–239 fertilizer production, gas enthalpies, 238–239, 240t heat transfers, 240t N2, 238 O2, 238 SO2, 238 SO3, 238 temperatures, 240t H2O production requirements, 259, 259f from SO3 gas, 104 industrial production, 11–12 acid composition, 11 bird-beak condensers, 11 ceramic retorts, 11 gold separation, 11 history, 11 lead chambers, 12 nitrogen processes, 12 silver separation, 11 single contact, 221–222, 222f from SO3 gas, 107–115 sulfate decomposition, 11 sulfur sources, 13t world demographics, 12, 12f, 15f intermediate making, 213 investment costs, 357–359 acid plants, 357–359 CEPCI, 358f modern plants, 2f nanoparticle injection, 289 Index prices, 14–15 falls in, 14 spikes, 14 spot, 16f production, 3–4 absorption towers, 4f acid strength compared to H2O strength, 259, 260–261, 260f, 261f alternative processes, 7–8 consumption averages, costs for, 360–361 exothermic reaction, first catalyst bed, 258, 260–261 flowsheet, 4, 5f gas-dehydration flows, H2O gas input, 253–254 H2O liquid requirements, 259, 259f interpretations of, 258–261 mass balances, 252–253, 257t mass water calculations, 255–258 metallurgical offgas, moist input gases, 254 moisture content, 261 as natural gas byproduct, output acid composition, 256 packed bed, 263t, 264t, 265t, 266t as petroleum byproduct, product acid water, 255 product from, recent developments, S mass balance, 255–256 single contact, 221–222, 222f, 252f SO3 input mass, 253, 258 spent acid decomposition, 261 spent acid regeneration, 6–7 from sulfur burning, 4–6 sulfuric acid output, 258 total balance, 256 vapors, smelter acid, 14 SO2, catalytic oxidation, 1–3 from SO3 gas absorption reaction mechanisms, 105–107 absorption towers, 105t, 108t, 110t, 111t, 112t, 113t acid coolers, 117f acid pumping, 104, 106f, 106t Index acid temperatures, 116 adjustments, 118t air dehydration, 107 candle filters, 114–115, 114f diffusion rates, 107 double contact, 118–120, 119f double contact production, 118–120, 119f as exothermic, 104 final, 120 gas dehydration, 107 gas temperatures, 116 industrial production, 107–115 input acid compositions, 115 input mass, 253, 258 intermediate, 120 operating temperatures, 106 operations, 116–118 output acid compositions, 115 residence times, 107 sensors, 118t shutdown, 116–117 single contact flowsheet, 104f startup, 116–117 steady control, 117–118 through water condensation, 104 spent, 14 composition masses, 49t compositions, 47–50 decomposition of, 51–52 dust removal, 54 flowsheets, 48f gas composition, 56 H2O content reduction, 47 handling of, 51 recycling, 56 SO2 oxidation, 54–56, 55t storage, 51 uses, 47 water-rich acids, 47 Sulfacid, 8, 293 SULFOX process, 292–293 third catalyst bed, 183 WSA process, 7–8, 284–285 acid droplet escape, 290–291 acid mist, 287 alternatives, 292–293 appraisal, 292 borosilicate glass, 290, 305 501 catalyst bed reactions, 287 catalytic composition, 285t coke chemical uses, 284t condensation mechanisms, 290, 302–305 condensers, 287, 289–291, 289f, 304f conventional acidmaking compared to, 291–292 equilibrium constant, 288f feed gas heating, 285 flowsheet, 285–287, 286f gas cooling, 285, 288, 290 industrial operations, 305 inorganic chemical processing, 284t liquid condensing, 287 minimum temperatures, 288 nanoparticle injection, 289 nonferrous metal extraction, 284t oil refining uses, 284t oxidized gas preparation, 288–289 petrochemical uses, 284t power industry uses, 284t pressure levels, 287 product acid composition, 291 raw material, 284 SO2 oxidation, 297–298 thermal behavior, 299 viscose fiber manufacture, 284t H2SO4 making catalytic plants, 77t, 78t, 79t, 80t, 81t, 82t enthalpy balances, 269–270 Heat recovery boilers, sulfur burning, 28 Heat recovery, from hot acid, 358, 361t Heat transfers, 236f bypassing, 246–247 with economizers, 245–246 percentage for, 246–247 bypassing with economizers, 245–246 gas enthalpies, 236f, 239 between catalyst beds, 240 H2SO4 making, 240t rates, 240–241 third catalyst bed, 239–240 Heatup paths after-H2SO4-making, 218t, 219f calculations, 216 equilibrium curve intercepts, 216–217 CO2 feed gases, 193, 194–196, 197 equilibrium-curve intercepts, 155f acid regeneration, 156 502 Heatup paths (Continued) catalyst beds, 153, 159, 159f catalyst degradation, 157 catalyst layers, 157 CO2 strength, 155–157, 157f exit gas composition, 159 feed gas, 151, 158f feed gas temperature, 153, 154f, 157 gas pressure, 154–155, 156f O2 strength, 155, 156f plots, 153f %SO2 oxidized-temperature points, 151–152, 152t SO2 strength, 157, 158–159, 158f first catalyst bed, 162f graphs, 202 N2 gas, 136f input quantities, 138–139 O2 gas, 136f input quantities, 136f second catalyst bed, 168–169, 169f, 175f bed differences, 168–169 enthalpy balances, 169 equilibrium, 170 exit gas composition, 170 graphs, 202 path point, 168, 175t preparation, 173 specific questions, 170 temperature measures, 168f SO2 gas, 136f adiabatic, 136 assumptions, 136 catalyst beds, 137f, 138f enthalpy balances, 140–142, 142t, 145 equilibrium curves, 149f feed gas composition, 136 feed gas strength effect, 145–147 feed gas temperature effect, 147–148 heat transfers, 136 input quantities, 138–139 level L quantity calculations, 142–143, 144t matrix calculations, 143 nitrogen molar balances, 139–140 oxidation calculation, 136, 137 oxidation to SO3, 84, 85f, 86f oxygen molar balances, 139–140 Index position significance, 148–149 preparation, 136, 143–145 slope significance, 148–149 sulfur molar balances, 139–140 temperature, 136 third catalyst bed, 184–186 volume percentages, 146t, 147f, 148f %SO2 oxidized-temperature points 1st catalyst bed, 154 equilibrium-curve intercepts, 151–152, 152t feed gas strength, 154 maximization of, 152 SO3 gas, 142t catalytic oxidation from SO2, 84, 85f, 86f, 137f, 138f enthalpy values, 142t feed gases, 190, 192t third catalyst bed, graphs, 202 HRS system, 47, 77t, 78t, 79t, 80t, 82t, 108t, 223t, 224t, 225t, 226t, 278, 350, 351f, 358 Hydrogen peroxide solutions, tail gas treatment, 333 I Industrial bypassing, 249 inefficiencies, 249 Industrial gas cooling first catalyst bed, 163–164 third catalyst bed, 183, 186f WSA process, 285, 288, 290 Industrial multicatalyst beds, 84–87 Industrial production H2SO4, 11–12 acid composition, 11 bird-beak condensers, 11 ceramic retorts, 11 gold separation, 11 history, 11 lead chambers, 12 nitrogen processes, 12 silver separation, 11 from SO3 gas, 107–115 sulfate decomposition, 11 sulfur sources, 13t world demographics, 12, 12f, 15f SO2 gas catalytic oxidation to SO3, 73–74, 87–89 Index Inorganic chemical processing, WSA process, 284t Input acid compositions acid temperature control, 272–273, 272f SO3 concentrations, output temperature influenced by, 273, 274f temperature effects, 273, 273f H2SO4 production, 115 SO2 gas heatup paths, 138–139 Input gas quantities after-H2SO4-making, 231, 232f condensers, in WSA process, 305, 306 enthalpies, 235–238 second catalyst bed, 170 N2 equation, 168 O2 equation, 168 SO2 equation, 168 SO3 equation, 168 Investment costs, H2SO4 production, 357–359 acid plants, 357–359 CEPCI, 358f metallurgical sulfuric acid plants, 360t K Ke function, temperature effects, 128, 129 L Lead chambers, 12 Level L second catalyst bed, 172–173 SO2 gas heatup path, 142–143, 144t Lime slurry, 330 LUREC process, 319–320, 320t M Magnesium processes, tail gas treatment, 333 Mass balances, H2SO4 production, 252–253, 257t Mass water calculations, H2SO4 production, 255–258 Materials of construction, 7, 66t, 67t, 68t, 69t, 77t, 78t, 79t, 80t, 81t, 82t, 223t, 224t, 225t, 226t, 280, 292, 334t, 336t, 349–356 MECS acid heat recovery systems, 351f Mercury removal, offgas scrubbing, 43 Metallurgical offgas See Offgas, metallurgical 503 Metallurgical sulfuric acid plants, 359 production costs, 361, 361t production rates, 360f Moist input gases, H2SO4 production, 254 Molar balances second catalyst bed, 171 SO2 gas nitrogen, 139–140 oxygen, 139–140 sulfur, 139–140 N N2 gas gas enthalpies, 238 heatup paths, 136f enthalpy values, 142t input quantities, 136f second catalyst bed, 168 SO2 catalytic oxidation to SO3, 126f sulfur burning, third catalyst bed, SO2 gas, 187 Na2CO3, 330 Nanoparticle injection, 299–302 flue gas concentration, 302 H2SO4 production, 289 methods, 300 optimum smoke concentration, 301–302 particle size, 302 particle-in-acid concentration, 302 smoke-in-flue gas concentration, 301 Natural gas, H2SO4 production from, Nitrogen oxides, 11–12, 114, 115, 339 Nitrogen processes CO2 feed gases, 195 H2SO4 production, 12 SO2 oxidation heatup paths, 139–140 tail gas removal processes, 326 Nonferrous metal extraction, WSA process, 284t O O2 gas decomposition furnaces, content effects, 54 equilibrium-curve intercepts, 155, 156f gas enthalpies, 238 heatup paths, 136f enthalpy values, 142t input quantities, 136f second catalyst bed, 168 504 O2 gas (Continued) SO2 catalytic oxidation to SO3, 74, 126f sulfur burning, 6, 27f third catalyst bed, SO2 gas, 184, 187 Offgas, metallurgical cleaning, 32f cooling, 32f, 34–35 with sprays, 35 dehydration, 60f dilution, 32f drying, 32f dust concentrations, 33, 34t from electrodes, 35 electrostatic collection, 35–36, 36f, 37f, 44 mist precipitation, 33 precipitator plants, 38t, 39t removal, 33 scrubbing, 33, 36 flowsheet, 32f gas cleaning plants, 40t heat recovery, 34–35, 35f scrubbing dust concentrations, 33, 36 Dynawave, 42f fluorine removal, 43 H2O removal, 43–44, 44f impure liquids, 43 mercury removal, 43 temperature after, 42 water, 37–43, 40t, 41t SO2 catalytic oxidation to SO3, 76t SO2 concentrations, 31–32, 34t gas conversion, 31 smelting, 31 standards, 33t sulfur burning, 27f temperatures, 34t Oil refining, WSA process, 284t Output acid composition acid temperature control adjustments, 274–275 SO3 concentrations, 273 H2SO4 production, 115, 256 Output gas condensers, in WSA process, 305, 306 enthalpies, 235–238 Oxygen CO2 feed gases, 194 SO2 oxidation heatup paths, 139–140 Index P Packed beds, H2SO4 production, 263t, 264t, 265t, 266t See also Catalyst beds Packing FLEXERAMIC, 70f structured, dehydration, 70f Particle-in-acid concentration, 302 Petroleum production H2SO4 production from, WSA process, 284t Phosphates, H2SO4 consumption, 13 Pipes, in acid plant construction materials, 353 Plant types copper smelting, dehydration, 67t, 68t SO2 catalytic reactions, startup for, 96 spent sulfuric acid, dehydration, 69t sulfur burning, dehydration, 60f, 66t zinc roaster, dehydration, 69t Power industry, WSA process, 284t Precipitators See Electrostatic precipitators Preconverters, 322, 323f Prices H2SO4 production, 14–15 falls in, 14 spikes, 14 spot, 16f SO2 catalytic reactions, 96 Product gas, sulfur burning, 23–28 composition, 24–27, 28 gas destination, 24 O2, 27f offgas temperatures, 27f SO2, 27f temperature control, 24–27, 28 Production See Industrial production Pumps elemental sulfur, 21–22 H2SO4 production acid, 104, 106f, 106t SO3 gas, 104, 106f, 106t R Recycling gas acid plant performance, 318 alternatives, 321–322 appraisal, 319 BAYQIK process, 322 calculations, 313–314 Index catalyst bed comparisons, 321, 321f effect of extent, 314–315 equilibrium, 317 equipment requirements, 319 feed gas, 317f feed gas dilution with air, 321–322, 322t first catalyst bed, 314f, 315f, 316f, 318f industrial SO3 applications, 319–321 LUREC process, 319–320, 320t objective, 313 oxidation rates, 315 preconverters, 322, 323f SO2, 317 temperature effects, 315–317, 316f third catalyst bed, 320f spent sulfuric acid, 56 S S mass balance, H2SO4 production, 255–256 Saddle packing dehydration, 59 designs, 65f reaction mechanisms, 64f gas dehydration, 64f Scrubbing processes metallurgical offgas dust concentrations, 33, 36 Dynawave, 42f fluorine removal, 43 H2O removal, 43–44, 44f impure liquids, 43 mercury removal, 43 temperature after, 42 with water, 37–43, 40t, 41t sulfur emissions, 344–345, 345t tail gas treatment, 328f, 331t, 334t, 336t Seawater scrubbers, tail gas treatment, 330 Second catalyst bed acid plants, 167 bed pressure, 204 calculations input points, 201f intercept points, 201f, 203f, 203t results, 199–200 specifications, 199, 200t CO2 feed gases, 202–203 enthalpy balances, 171–172, 172t heatup path, 169 gas enthalpies, 238 505 gas input temperature, 163 graphs, 201–202 heatup paths, 202 SO2 oxidation efficiency, 202 heat loss assumptions, 208–209, 209f heatup path, 168–169, 169f, 175f bed differences, 168–169 enthalpy balances, 169 equilibrium, 170 exit gas composition, 170 graphs, 202, 203f path point, 168, 175t preparation, 173 specific questions, 170 temperature measures, 168f input gas, 170, 207f N2 equation, 168 O2 equation, 168 SO2 equation, 168 SO3 equation, 168 temperatures, 207 intercept point attainment assumption, 209 calculations, 201f, 203f, 203t level L calculations, 172–173 matrix calculations, 173 molar balances, 171 O2 in feed gas, 206 volume effects, 206f schematic, 162f SO2 catalytic reactions, 97f, 99f in feed gas, 204–206, 204f, 205f production process, 207 %SO2 definition, 167 worksheet, 174t SO2 oxidation applicability proof, 178 efficiency with gas cooling, 180f equilibrium curve equation, 177–178 graph efficiency, 202 intercepts, 178–180 multibed efficiency, 180 temperature points, 179t values, 208f SO3 in feed gas, 202 steady-state assumptions, 208 temperature, 173 heatup path, 168f 506 Sensible heat recovery, 276–278, 279–280 commercial systems, 280 schematic, 277f Silver, H2SO4 production, 11 Single contact acid plants, 343 Single contact H2SO4 production, 221–222, 222f flowsheet, 252f SiO2, in SO2 catalytic reactions, 96 Smelter acid, 14 Smoke-in-flue gas concentration, 301 SO2 gas See also Dehydration after-H2SO4-making, 220f, 230 double contact, 230 efficiency, 217–221, 232f fifth catalyst bed, 231f fourth catalyst bed, 230f catalytic oxidation to SO3, 1–3 acid plant feed gases, 2t bed pieces, 74f catalysts, controls, 88 converters, 3f, 85f, 86f double contact acidmaking, 87 equilibrium constant, 83f, 125–127 feed gas, 74, 76t, 190 feed gas drying, 2–3 furnace offgases, 76t H2SO4 making catalytic plants, 77t, 78t, 79t, 80t, 81t, 82t heatup paths, 84, 85f, 86f, 137f, 138f hydrocarbon fuel combustion, 88np industrial, 73–74, 87–89 industrial multicatalyst beds, 84–87 maximum function, 76, 83f N2 gas, 126f necessities for, 75–84 O2 gas, 126f, 130, 131f O2 sources, 74 recent advances, 89 schematic, 75f shutdown of, 88–89 startup for, 87–88 steady operations, 88 vanadium oxide, 84, 89 wet, 2np catalytic reactions, 91–95, 92f advantages, 93t bed temperatures, 99–100, 99f Index bed thickness, 97–98 chemical changes, 96 composition, 95–96 Cs2S2O7-V2O5 phase diagrams, 97t deactivation, 95np, 95 diameter, 97–98, 98f first bed, 97f, 99f gas, 92–94 installation, 96 maintenance, 100 manufacture, 95–96 maximization, 92–94 melting, 96 molten, 92 operating temperatures, 95 plant startup, 96 prices, 96 rapid, between gases and ions, 92 reactivation, 95 residence times, for gas, 98–99 screening, 100 second bed, 97f, 99f shapes, 96–97 SiO2, 96 size choices, 96–97 temperature effects, 94f third bed, 97f, 99f uses, 93t vanadium oxide, 91, 96 equilibrium catalytic oxidation to SO3, 83f, 125–127, 187 curves, 149f heatup path intercepts, 157, 158–159, 158f first catalyst bed, 97f, 99f catalytic reactions, 97f, 99f cooldown path, 161–164, 163f feed gas, 161, 204–206, 204f, 205f graph efficiency, 202 inefficiencies, 161 values, 208f gas enthalpies, 238 gas recycling, 317 in H2SO4, heatup paths, 136f adiabatic, 136 assumptions, 136 catalyst beds, 137f, 138f Index enthalpy balances, 140–142, 142t, 145 equilibrium curves, 149f feed gas composition, 136 feed gas strength effect, 145–147 feed gas temperature effect, 147–148 heat transfers, 136 input quantities, 138–139 level L quantity calculations, 142–143, 144t matrix calculations, 143 nitrogen molar balances, 139–140 oxidation calculation, 136, 137 oxygen molar balances, 139–140 position significance, 148–149 preparation, 136, 143–145 slope significance, 148–149 sulfur molar balances, 139–140 temperature, 136 volume percentages, 146t, 147f, 148f second catalyst bed, 168 applicability proof, 178 catalytic reactions, 97f, 99f efficiency with gas cooling, 180f equilibrium curve equation, 177–178 in feed gas, 204–206, 204f, 205f graph efficiency, 202 intercepts, 178–180 multibed efficiency, 180 production process, 207 temperature points, 179t values, 208f spent sulfuric acid, 54–56, 55t sulfur burning, 6, 27f sulfur emissions, 342–343 industrial oxidation, 341–343, 342f, 344f, 346t tail gas removal processes, 325, 327f third catalyst bed catalytic reactions, 97f, 99f cooldown path, 183–184, 185f efficiency increases, 186f equilibrium curve intercept, 187 in feed gas, 204–206, 204f, 205f gas cooling, 183, 186f graph efficiency, 202 graphical representation, 187 heatup path, 184–186 input gas temperature, 184, 187 N2 inputs, 187 507 O2 inputs, 184, 187 production process, 207 schematic, 184f SO3 inputs, 184, 187 values, 208f WSA process, 295–299, 298f %SO2 oxidized-temperature points, heatup paths 1st catalyst bed, 154 equilibrium-curve intercepts, 151–152, 152t feed gas strength, 154 maximization of, 152 SO3 gas acid temperature control input, 273, 274f catalytic oxidation from SO2, 1–3 acid plant feed gases, 2t bed pieces, 74f catalysts, controls, 88 converters, 3f, 85f, 86f double contact acidmaking, 87 drying of feed gas, 2–3 equilibrium constant, 83f feed gas, 74, 76t, 190 furnace offgases, 76t H2SO4 making catalytic plants, 77t, 78t, 79t, 80t, 81t, 82t heatup path, 84, 85f, 86f, 137f, 138f hydrocarbon fuel combustion, 88np industrial, 73–74, 87–89 industrial multicatalyst beds, 84–87 maximum function, 76, 83f necessities for, 75–84 O2 gas, 126f, 130, 131f O2 sources, 74 recent advances, 89 schematic, 75f shutdown of, 88–89 startup for, 87–88 steady operations, 88 vanadium oxide, 84, 89 wet, 2np equilibrium catalytic oxidation from SO2, 83f curve equation, in feed gases, 189–190, 193 feed gases, 189–193 changed balances, 191–192 enthalpy balances, 191 508 SO3 gas (Continued) equilibrium curve equation, 189–190, 193 first catalyst bed, 202 heatup path matrix, 190, 192t second catalyst bed, 202 SO2 input equation, 190 third catalyst bed, 202 first catalyst bed, in feed gas, 202 gas enthalpies, 238 gas recycling, industrial applications, 319–321 H2SO4 production, 253, 258 absorption reaction mechanisms, 105–107 absorption towers, 105t, 108t, 110t, 111t, 112t, 113t acid coolers, 117f acid mist, 107–115, 114f acid pumping, 104, 106f, 106t acid temperatures, 116 adjustments, 118t air dehydration, 107 candle filters, 114–115, 114f diffusion rates, 107 double contact, 118–120, 119f as exothermic, 104 final, 120 gas dehydration, 107 gas temperatures, 116 industrial production, 107–115 input acid compositions, 115 intermediate, 120 operating temperatures, 106 operations, 116–118 output acid compositions, 115 residence times, 107 sensors, 118t shutdown, 116–117 single contact flowsheet, 104f startup, 116–117 steady control, 117–118 through water condensation, 104 heatup path, 142t catalytic oxidation from SO2, 84, 85f, 86f, 137f, 138f enthalpy values, 142t second catalyst bed, in feed gas, 202 third catalyst bed, 184, 187 in feed gas, 202 Index Sodium ash See Na2CO3 Spent acid decomposition, in H2SO4 production, 261 Spent acid regeneration flowsheets, 48f H2SO4 production, 6–7 Spent sulfuric acid, 14 composition masses, 49t compositions, 47–50 decomposition furnace, 49f, 51–52 O2 content effects, 54 operations, 50t, 53–54, 53f products, 52 temperature effects, 53 decomposition of, 51–52 dehydration plants, 60f, 69t dust removal, 54 flowsheets, 48f gas composition, 56 H2O content reduction, 47 handling of, 51 recycling, 56 SO2 oxidation, 54–56, 55t storage, 51 uses, 47 water-rich acids, 47 Sprays, offgas cooling, 35 Stainless steel, in acid plants, 351 Steam injection, acid temperature control, 279 advantages, 279 H2O input requirements, 279 Steam production, 278 Stick test, 347f Storage, spent sulfuric acid, 51 Structured packing, dehydration, 70f Sulfacid, 8, 293 Sulfate decomposition, H2SO4 production, 11 SULFOX process, 292–293 Sulfur elemental atomizers, 22–23 delivery, 21–22 furnaces, 22–23 H2SO4 production, melting point, 20 pipes for, 21–22 pumps for, 21–22 viscosity, 20–21, 21f Index emissions acid plants, 342t, 343t, 344f acid tower operation, 346–347 catalyst selection, 343 catalytic kinetics, 341–342 composition, 345–346 control, 346, 347 double contact, 343, 345t equilibrium compared to SO2 oxidation, 342–343 industrial SO2 oxidation, 341–343, 342f, 344f, 346t methods, 343–347 mist eliminators, 346–347 regulations, 342 single contact, 343 steady feed gas flow, 345–346 stick test, 347f by sulfur source, 346t tail gas scrubbing, 344–345, 345t SO2 oxidation heatup paths, 139–140 sources, 13t superheater, 25t from tail gas characteristics, 326–328 composition, 326–327 emissions, 344–345, 345t environmental standards, 325–326, 326t pressure, 328 reheating processes, 328 temperature, 327–328 Sulfur burning, 4–6, 20–21 acid plants, 360–361 atomizers, 22–23 carbon impurity, 20 dehydration, 60f plant types, 60f, 66t dried air supply, 22 flowsheet, 20f furnaces, 19f, 22–23, 23f, 25t heat recovery boilers, 28 heat transfer, 24f main blowers, 22–23 molten delivery, 21–22 N2 gas, O2 gas, product gas, 23–28 composition, 24–27, 28 gas destination, 24 509 O2, 27f offgas temperatures, 27f SO2, 27f temperature control, 24–27, 28 SO2 gas, viscosity, 20–21 Sulfur burning acid plants, 360–361, 361t Sulfur dioxide See SO2 gas Sulfur trioxide See SO3 gas Sulfuric acid See H2SO4 T Tail gas industrial treatment methods, 328–336 with ammonia, 333 by-product-producing processes, 333–336 Cansolv process, 334 CaSO3, 329 CaSO4, 330 chemical reactions, 329–330 concentrated mode systems, 333 costs, 338 dilute mode systems, 333 disposal issues, 338 Dowa process, 333 dual alkali systems, 330, 333 with hydrogen peroxide solutions, 333 lime slurry, 330 magnesium processes, 333 with Na2CO3, 330 performance requirements, 337 process operating conditions, 337 reliability, 338 scrubbing processes, 328f, 331t, 334t, 336t seawater scrubbers, 330 site-specific factors, 338 tower designs, 329f waste-producing processes, 330–333 removal processes acid mist, 325–326, 327 nitrogen, 326 SO2, 325, 327f sulfur from characteristics, 326–328 composition, 326–327 emissions, 344–345, 345t environmental standards, 325–326, 326t 510 Tail gas (Continued) pressure, 328 reheating processes, 328 temperature, 327–328 Temperature controls condensers, in WSA process, 305–306 decomposition furnaces, 53 offgas scrubbing, 42 product gas, in sulfur burning, 24–27 WSA process, H2SO4 production, 288 Temperature effects acid temperature control, 273, 273f after-H2SO4-making, 219t on construction materials for acid plants, 350 gas recycling, 315–317, 316f calculation methods, 316f H2SO4 acid temperatures, 116 from SO3 gas, 116 heatup paths, in second catalyst bed, 168f SO2 catalytic reactions, 94f bed temperatures, 99–100, 99f equilibrium constants, 129–131 heatup paths, 136 second catalyst bed, 179t SO3 oxidation from SO2, 75–84 Third catalyst bed bed pressure, 204 calculations input points, 201f intercept points, 201f, 203f, 203t results, 199–200 specifications, 199, 200t CO2 feed gases, 202–203 gas enthalpies, 237t heat transfers, 239–240 gas recycling, 320f graphs, 201–202 heatup paths, 202, 203f SO2 oxidation efficiency, 202 H2SO4 making reaction, 183 heat loss assumptions, 208–209, 209f heatup path graphs, 202, 203f input gas, 207f temperatures, 207 intercept point attainment assumption, 209 calculations, 201f, 203f, 203t Index O2 in feed gas, 206 volume effects, 206f SO2 catalytic reactions, 97f, 99f in feed gas, 204–206, 204f, 205f production process, 207 SO2 oxidation cooldown path, 183–184, 185f efficiency increases, 186f equilibrium curve intercept, 187 gas cooling, 183, 186f graph efficiency, 202 graphical representation, 187 heatup path, 184–186 input gas temperature, 184, 187 N2 inputs, 187 O2 inputs, 184, 187 schematic, 184f SO3 inputs, 184, 187 values, 208f SO3 in feed gas, 202 steady-state assumptions, 208 Towers, processes in H2SO4 production, 12 See also Absorption towers V Vanadium oxide catalytic reactions, SO2 oxidation, 91, 96 SO2 catalytic oxidation to SO3, 84, 89 Vapors, H2SO4 production, Viscose fiber manufacture, WSA process, 284t Viscosity elemental sulfur, 20–21, 21f sulfur burning, 20–21 W Water See H2O (liquid) Water-rich acids, 47 Wet catalysis, SO2 to SO3 oxidation, 2np Wet gas Sulfuric Acid (WSA) process acid composition, 291 appraisal condensers, 309–310 H2SO4 production, 292 characteristics, 296t catalyst, 93t, 283, 295 condensers acid collection, 306 Index acid composition, 291, 307 acid production rates, 308–309 appraisal, 309–310 condensate composition, 307, 308t gas velocity, 309, 309t H2SO4 production, 287, 289–291, 289f, 304f input gas temperature, 305, 306 output gas temperature, 305, 306 reactions, 306 re-evaporation of H2O, 307–308 residence time, 309, 309t temperature choices, 305–306 environmental emissions, 300f feed gas concentrations, 297 H2SO4 production, 285 flowsheets, 285–287, 286f, 300f H2O effects, 296–297, 297f H2SO4, 7–8, 284–285 acid droplet escape, 290–291 acid mist, 287 alternatives, 292–293 appraisal, 292 borosilicate glass, 290, 305 catalyst bed reactions, 287 catalytic composition, 285t coke chemical uses, 284t condensation mechanisms, 290, 302–305 condensers, 287, 289–291, 289f, 304f conventional acidmaking compared to, 291–292 equilibrium constant, 288f feed gas heating, 285 feed gas SO2 limits, 325, 326t flowsheet, 285–287, 286f 511 gas cooling, 285, 288, 290 industrial operations, 305 inorganic chemical processing, 284t liquid condensing, 287 minimum temperatures, 288 nanoparticle injection, 289 nonferrous metal extraction, 284t oil refining uses, 284t oxidized gas preparation, 288–289 petrochemical uses, 284t power industry uses, 284t pressure levels, 287 product acid composition, 291 raw material, 284 SO2 oxidation, 297–298 thermal behavior, 299 viscose fiber manufacture, 284t nanoparticle injection, 299–302 flue gas concentration, 302 H2SO4 production, 289 methods, 300 optimum smoke concentration, 301–302 particle size, 302 particle-in-acid concentration, 302 smoke-in-flue gas concentration, 301 SO2 oxidation, 295–299, 298f feed gases, 298f H2SO4 formation, 297–298 objectives, 295–296 total increases, 298 WSA process See Wet gas Sulfuric Acid process Z Zinc roaster plants, 69t [...]... contact with strong sulfuric acid (Fig 1.4) About 10% of sulfuric acid is made this way Virtually, all is reused for petroleum refining and polymer manufacture 1.7 Sulfuric acid product Most industrial acid plants have three flows of sulfuric acid one gas-dehydration flow and two H2SO4(ℓ)-making flows These flows are connected through automatic control valves to: (a) maintain proper flows and H2SO4(ℓ) concentrations... and plastics 3 Pigments 2 Pulp and paper 2 14 Sulfuric Acid Manufacture Sulfuric acid is also used extensively for making other fertilizers (e.g., sulfates) and chemicals of all sorts 2.2 Acid plant locations Sulfuric acid plants are located throughout the industrialized world (Fig 2.2) Most are located near their product acid s point of use, i.e., near fertilizer plants, copper ore leach plants, and. .. oxidation, and H2SO4(ℓ) making 1.6 Spent acid regeneration A major use of sulfuric acid is as catalyst for petroleum refining and polymer manufacture (Chapter 5) The acid becomes contaminated with water, hydrocarbons, and other compounds during this use It is regenerated by: (a) spraying the acid into a hot ($1050 C) furnace—where the acid decomposes to SO2, O2, and H2O(g) (b) cleaning, drying, and heating... transport of the product acid to fertilizer plants in Florida Another example of this is the production of acid at Cu smelters in Sonora, Mexico, and Arizona, United States, and rail and truck transport of product acid to numerous copper ore leaching operations in Arizona and New Mexico, United States, and Sonora, Mexico Production of pure sulfuric acid from contaminated “spent” sulfuric acid catalyst is almost... H2O(g), SO2, O2, N2 gas and: (b) condenses strong ($98 mass% H2SO4(ℓ) À 2 mass% H2O(ℓ)) sulfuric acid directly from this oxidized gas 8 Sulfuric Acid Manufacture It is described in Chapters 25 and 26 In 2013, it is mainly used for removing SO2 from moist, dilute ($3 volume% SO2) waste gases (Chapter 25) It accounts for $ 3% of world sulfuric acid production 1.9.2 Sulfacid® About 20 Sulfacid® installations... by: (a) a sharp increase in China’s demand for metals and chemicals, all of which require sulfuric acid for their manufacture (b) inability of the world’s sulfuric acid producers to rapidly increase their acid production rate, i.e., their inability to meet this increased demand The 2009 catastrophic price fall was the reverse of the above China’s demand for metals and chemicals decreased briefly, but... 6.1% Figure 2.2 World production of sulfuric acid, % by region (Gustin, K., personal communication, January 2012) Total 2011 world production was over 200 million tonnes of contained H2SO4 15 16 Sulfuric Acid Manufacture Sulfuric acid price (US$ per tonne) U.S Gulf spot sulfuric acid 400 300 200 100 0 2003 2005 2007 Year 2009 2011 Figure 2.3 Spot price for sulfuric acid at U.S Gulf of Mexico ports (Boyd,... strengthened acid to dilution, recycle, and market H 2SO4 strengthened acid to dilution, recycle, and market 5 Figure 1.4 Double contact sulfuric acid manufacture flowsheet The three main SO2 sources are at the top Sulfur burning is by far the biggest source The acid product leaves from two H2SO4(ℓ) making towers at the bottom Barren tail gas leaves the final H2SO4(ℓ) making tower, right arrow 6 Sulfuric Acid. .. sulfide minerals (c) decomposing contaminated (spent) sulfuric acid catalyst Elemental sulfur is far and away the largest source Table 1.1 describes three typical sulfuric acid plant feed gases It shows that acid plant SO2 feed is always mixed with other gases Sulfuric acid is almost always made from these gases by: (a) catalytically reacting their SO2 and O2 to form SO3(g) (b) reacting (a)’s product SO3... with the H2O(ℓ) in 98.5 mass% H2SO4(ℓ), 1.5 mass% H2O(ℓ) sulfuric acid Industrially, both processes are carried out rapidly and continuously (Fig 1.1) The standard state for SO2, SO3, O2, N2, and CO2 is gas in the acid plant Each is referenced in this book, for example, as O2 not O2(g) The standard state for H2O, S, and H2SO4 is gas or liquid in the acid plant Each is referenced accordingly 1.1 Catalytic