Report No. 59 ALIPHATIC SURFACTANTS by MIKIO KUMAGAI and SHIGEYOSHI TAKAOKA December 1969 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I I MENLO PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION......................... 1 2 SUMMARY........................... 3 3 INDUSTRY STATUS........,,............. 11 4 ALPHA OLEFIN SULFONATES......,..........,. 33 Introduction... 33 Chemistry... 33 Reaction Mechanism... 33 Kinetics... 37 Review of Processes... 37 Feed Specification... 47... 49 Neutralization and Hydrolysis... 50 Bleaching... 52 Process Description... 52 Process Discussion... 58 Cost Estimates... 66 Capital Costs... 66 Production Costs... 66 5 ALKANE SULFONATES...................... 73 Introduction........................ Chemistry....................... Alkane Sulfonates by Sulfoxidation of n-paraffins... Alkane Sulfonates from Alpha Olefins and Sodium Bisulfite Alkane Sulfonates by Sulfochlorination of n-paraffins.. Alkane Sulfonates by Other Methods............ Review of Processes....,............... Alkane Sulfonates by Sulfoxidation of n-paraffins.... Alkane Sulfonates from Alpha Olefins and Sodium Bisulfite Alkane Sulfonates by Sulfochlorination of n-paraffins.. Process Description.................... Process Discussion..................... Cost Estimates....................... Capital Investment,................... Production Costs...................... 73. 74. 74. 76. 78. 78. 79. 79. 89. 94. 98. 107. 109. 109. 109
CONTENTS PRIMARY ALKYL SULFATES... '.... Introduction... Chemistry Review of Processes... SECONDARY ALKYL SULFATES... Introduction... Chemistry... Review of Processes... PRIMARY ALCOHOL ETHOXYLATES AND ETHOXYLSULFATES... Introduction... Chemistry... Ethoxylation... Sulfation... Review of Processes... Ethoxylation of Primary Alcohols... Sulfation of Primary Alcohol Ethoxylate... Process Description... Primary Alcohol Ethoxylate (9EO)... Primary Alcohol Ethoxysulfate (3EO)... Process Discussion... Primary Alcohol Ethoxylate (9EO)... Primary Alcohol Ethoxysulfate (3EO)... Cost Estimates... Capital Cost... Production Costs... SECONDARY ALCOHOL ETHOXYLATES AND ETHOXYSULFATES... Introduction... Chemistry... Review of Processes... Ethoxylation of Secondary Alcohols... Sulfation of Secondary Alcohol Ethoxylate... Process Description... Secondary Alcohol Ethoxylate (9EO)... Secondary Alcohol Ethoxysulfate (3EO)... Process Discussion... Secondary Alcohol Ethoxylate (9EO)... Secondary Alcohol Ethoxysulfate (3EO)... 115 115 116 118 129 129 130 132 137 137 139 139 144 147 147 155 157 157 164 169 169 170 172 172 172 181 181 183 184 184 187 189 190 197 201 201 202 vi
CONTENTS 9 (continued) Cost Estimates... 202 Capital Cost... 202 Production Costs... 203 APPENDIX A DESIGN AND COST BASIS................ 211 APPENDIX B DETERGENCY AND BIODEGRADABILITY........... 215 APPENDIX C RAW MATERIAL AND PRODUCT SPECIFICATIONS,...... 245 APPENDIX D SAFETY AND HANDLING.....,........... 251 CITEDREFERENCES...........,............. 257 PATENT REFERENCES BY COMPANY........,.......... 283 vii
ILLUSTRATIONS 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 5.1 5.2 5.3 8.1 8.2 8.3 9.1 9.2 Reaction of Alpha Olefins with Sulfur Trioxide-Dioxane. Effect of Temperature on Alpha Olefin Conversion to Alpha Olefin Sulfates and Disulfonate., Effect of Time on Alpha Olefin Conversion to Alpha Olefin Sulfonates and Disulfonate........,..................... Temperature Profile of C17 Average Chain Length Olefin. Temperature Increment from Alpha Olefin Introduction Temperature to Peak Temperature............ Temperatures Maintained in Second Reaction Temperature Zone...,....,....... Effect of Alpha Olefin and Sulfur Trioxide Cost on Production Cost of Alpha Olefin Sulfonates....... Production Cost.........,.......... Mechanism of Sulfoxidation of n-paraffins,...... Alkane Sulfonate by Sulfoxidation........... Alkane Sulfonate by Sulfoxidation (Light Water Process) Production Cost.................... Primary Alcohol Ethoxylates and Ethoxysulfates..... Primary Alcohol Ethoxylates (9EO) Production Cost.................... Primary Alcohol Ethoxysulfates (3EO) Production Cost.................... Secondary Alcohol Ethoxylates and Ethoxysulfates.... Secondary Alcohol Ethoxylates (9EO) Production Cost.......,........,.,... 34.. 38.. 39.. 55.. 60,. 61.. 62.. 70.. 71.. 75.. 101.. 113.. 161.. 178... 179.. 193,. 208 ix
ILLUSTRATIONS 9.8 B.l B.2 B.3 B.4 B.5 B.6 B.7 B.8 B.9 B.10 B.11 B.12 B.13 B.14 B.15 B.16 B.17 Secondary Alcohol Ethoxysulfates (3EO) Production Cost..........,......,..., Detergency of AOS, LAS, and AS Built and Nonbuilt Formulations.,..,...,.,....,........ Rate of Biodegradation......,............ Detergency of Heavy-Duty Detergent Formulations...... Relative Detergency of AOS and LAS............. Biodegradability of AOS and LAS.............. Detergency vs Carbon Number and Hardness-Formulated SAS.. Detergency Ratings of Single Carbon Number Primary Alcohol Sulfates....,..,.............. Comparative Biodegradability of Alkyl Sulfates....... Cold Water Fabric Detergency of Alcohol Ethoxylates.... Comparative Biodegradability--Anionics (Semicontinuous Activated Sludge Test),....,.......,..... Comparative Biodegradability-- Nonionics (Shake Flask Test), Comparative Biodegradability-- Anionics (Shake Flask Test). Variation in Rate of Degradation of n-dodecanol Ethoxylates with Ethylene Oxide Content.,...,.... Variation in Rate of Degradation with Hydrophobic Chain Length.,...................... Variation in Rate of Degradation with Position of Secondary Attachment...,................ Biodegradability of Polyoxyethylene Alcohols in River Die-Away Test Using Foam as Criterion..,........ Biodegradability of Polyoxyethylene Alcohols in River Die-Away Test....................... B.18 Comparison of Biodegradability of Linear Alcohol Ethoxylates with Other Detergents............. 242 B.19 Comparison of Biodegradability of Linear Alcohol Ethoxysulfate with Other Detergents............ 243 209 216 218 219 220 221 223 228 230 231 232 233 234 235 236 239 240 241 X
TABLES 2.1 3.1 4.1 4.2 4.3 4.4 4.5 4.6 5.1 5.2 5.3 5.4 5.5 5.6 5.7 Various Aliphatic Surfactants Summary of Costs.,.,................. 7 U.S. Producers of Primary Alcohol Sulfates, Ethoxylates and Ethoxysulfates.,............,..... 20 Product Distribution in of Alpha Olefins in a Continuous Falling Film Reactor.............. 40 Alpha Olefin Sulfonates by Direct of Alpha Olefin with Sulfur Trioxide Patent Summary...,............,..... 41 Major Process Equipment and Utilities Summary.,,.,.. 55 Stream Flows..,..,,..........,..... 57 Total Capital Investment,..,,............ 67 Production Costs....,................ 68 Alkane Sulfonates by Sulfoxidation Patent Summary...................... 81 Alkane Sulfonates from Alpha Olefins and Sodium Bisulfite Patent Summary...................... 91 Alkane Sulfonates by Sulfochlorination of n-paraffin Patent Summary............,.,....... 95 Alkane Sulfonates by Sulfoxidation (Light Water Process) Major Process Equipment and Utilities Summary....... 101 Alkane Sulfonates by Sulfoxidation (Light Water Process) Stream Flows...............,....... 105 Alkane Sulfonates by Sulfoxidation Total Capital Investment,.............,.. 110 Alkane Sulfonates by Sulfoxidation (Light Water Process) Production Costs..,...,.............. 111 xi
TABLES 6.1 7.1 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 9.1 9.2 9.3 9.4 9.5 and Sulfation Processes Patent Summary...................... 119 Secondary Alkyl Sulfate by Sulfation of Olefin with Sulfuric Acid Patent Summary,..................... 133 Primary Alcohol Ethoxylates and Ethoxysulfates Patent Summary,..................... 149 Primary Alcohol Ethoxylate 9EO) Major Process Equipment and Utilities Summary....... 161 Primary Alcohol Ethoxylate (9EO) Stream Flows,....,................. 163 Primary Alcohol Ethoxysulfate (3EO) Major Process Equipment and Utilities Summary....... 166 Primary Alcohol Ethoxysulfate (3EO) Stream Flows.,...................., 167 Primary Alcohol Ethoxylate (9EO) Total Capital Investment.........,....... 174 Primary Alcohol Ethoxysulfate (3EO) Total Capital Investment.....,...,....... 175 Primary Alcohol Ethoxylate (9EO) Production Costs.......,.....,....... 176 Primary Alcohol Ethoxysulfate (3EO) Production Costs..................,.. 177 Secondary Alcohol Ethoxylates and Ethoxysulfates PatentSummary...................... 185 Secondary Alcohol Ethoxylate (9EO) Major Process Equipment and Utilities Summary.....,. 193 Secondary Alcohol Ethoxylate (9EO) Stream Flows...,...,............... 195 Secondary Alcohol Ethoxysulfate (3EO) Major Process Equipment and Utilities Summary....... 198 Secondary Alcohol Ethoxysulfate (3EO) Stream Flows...,..,.,......,....... 199 xii
TABLES 9.6 Secondary Alcohol Ethoxylate (9EO) Total Capital Investment.,.....,......,., 204 9.7 Secondary Alcohol Ethoxysulfate (3EO) Total Capital Investment................. 205 9.8 Secondary Alcohol Ethoxylate (9EO) Production Costs.....,............... 206 9.9 Secondary Alcohol Ethoxysulfate (3EO) Production Costs..,....,............. 207 xiii