Report No. 99
ACRYLAMIDE AND POLYACRYLAMIDE
by YEN-CHEN YEN e
June 1976 a A private report by the
PROCESS ECONOMICS PROGRAM l STANFORD RESEARCH INSTITUTE MENLO PARK. CALIFORNIA I a CONTENTS
1 INTRODUCTION ...... , ......
2 SUMMARY ...... 3 Acrylamide ...... 4 General Aspects ...... 4 Technical Aspects ...... 6 Acrylamide Polymers ...... 7 General Aspects ...... 7 Technical Aspects ...... 12
3 INDUSTRY STATUS ...... 19 Production Capacity ...... 19 Production and Consumption ...... 19 Commercial Acrylamide 24 Commercial Polyacrylamidls' ...... 24
4 APPLICATIONS OF ACRYLAMIDE AND POLYACRYLAMIDE ...... 27 As Flocculants ...... 27 For Waste Water Treatment ...... 27 For Potable Water Treatment ...... 29 For Various Process Industries ...... 29 For the Mining Industry ...... 29 In Oil Production ...... 30 Mobility Control Agent'& Wa;e; kodi;g'for Oil Recovery 30 Additive for Oil Well Drilling Fluids ...... 31 Aid in Fracturing, Acidifying, and Other'Operations Relating to Oil Production ...... 32 In the Paper and Pulp Industry ...... 33 Additives for Paper ...... 33 Coating for Paper ...... 35 Other Uses in the Paper and Pulp Industry ...... 36 In the Textile Industry ...... 36 Coating for Materials Other than Paper and Textiles ..... 38 Construction and Civil Engineering Uses ...... 38 Adhesives ...... 39 Agricultural Uses ...... 39 Plastics or Plastics Additives ...... 40 OtherUses ...... 40
- 5 COMPARISON OF PROCESSES ...... 43 Making Acrylamide ...... 43 Polymerization Processes ...... 46 Producing Anionic Polyacrylamides ...... 46 Polymerization at Site with Purchase of Polymer ...... 48
0 Vii CONTENTS
6 ACRYLAMIDE BY THE SULFURIC ACID PROCESS ...... 53 Chemistry ...... 53 Review of Processes ...... 53 Process Description ...... 62 Process Discussion ...... 68 Cost Estimate ...... 68
7 ACRYLAMIDE BY CATALYTIC HYDRATION OF ACRYLONITRILE . . . . . 73 Chemistry ...... 73 Review of Pa&n; literature ...... 73 Reactant and Reaction Medium ...... 83 Catalyst ...... 83 Reaction CoAditions...... 84 Recovery of Acrylamide ...... 84 An Electrochemical Procesi ...... 85 Process Evaluations ...... 85 A Fixed Bed Catalyst Process ...... 86 Process Description ...... 86 Process Discussion ...... 92 Cost Estimate ...... 92 A Suspended Catalyst Process ...... 96 Process Description ...... 96 Process Discussion ...... 102 Cost Estimate ...... 102 Conversion of 50% Solution to Solid Acrylamide ...... 102
8 POLYMERIZATION OF ACRYLAMIDE ...... 109 Mechanism ...... 109 Catalyst for Polymerization ...... 110 Inorganic Compounds Acting Alone ...... 111 Organic Compounds Containing P, B, As,orMetals 111 Organic Compounds ...... 111 Redox Compounds ...... 112 Kinetics ...... 115 Polymerization Processes ...... 118 Bulk Polymerization ...... 118 Solution Polymerization ...... 119 Precipitation Polymerization ...... 130 Suspension Polymerization ...... 132 Emulsion Polymerization ...... 132
. . . Vlll CONTENTS
8 POLYMERIZATION OF ACRYLAMIDE (Continued) Feedstock for Polymerization ...... 136 Polymerization Equipment ...... 140 Removal of Residual Monomer 143 Photo-activated Polymerization' ...... 143 Radiation Polymerization ...... 144 Polymerization with Other Kinds of Initiation ...... 148
9 EVALUATION OF PROCESSES FOR ACRYLAMIDE POLYMERIZATION ... 149 A Solution Process for Medium Molecular Weight Polyacrylamide 149 Process Description...... 149 Process Discussion ...... 154 Cost Estimate ...... 155 A Solution Process for High Molecular Weight Polyacrylamide ...... 155 Process Description ...... 155 Process Discussion ...... 162 Cost Estimate ...... 163 A Solution Process'for'V$ $h'MAlecular Weight Polyacrylamide ...... 163 Process Descriptio; ...... 163 Process Discussion ...... 171 Cost Estimate ...... 171 A Solution Process'fir Eitremeiy'High Molecular Weight Polyacrylamide ...... 175 Process Description ...... 175 Process Discussion ...... 180 Cost Estimate .. 180 An Emulsion Procesi for Polyic;yiamide...... 180 Process Description ...... 180 Process Discussion ...... 188 Cost Estimate ...... 189 A Precipitation Process for Polyacrylamide ...... 189 Process Description ...... 189 Process Discussion ...... 197 Cost Estimate ...... 197
10 DERIVATIVES OF POLYACRYLAMIDE ...... 201 Review of Products and Processes ...... 201 Partially Hydrolyzed Polyacrylamide ...... 201 Methylolated Polyacrylamide ...... 205
ix CONTENTS
10 DERIVATIVES OF POLYACRYLAMIDE (Continued) Sulfomethylated Polyacrylamide ...... 207 Mannich Reaction Product ...... 209 Hoffman Degradation Product ...... 209 Other Cationic Polyacrylamides ...... 211 Insoluble Polyacrylamides ...... 214 Grafted Polyacrylamides ...... 216 Other Derivatives ...... 216 Process Evaluations ...... 216 Anionic Polyacrylamide by Simultaneous Polymerization and Hydroysis ...... 216 Process Description ...... 216 Cost Estimate ...... 222 A Process for Making Partially Hydrolyzed Polyacrylamide With Very High Molecular Weight ...... 226 Process Description ...... 226 Cost Estimate ...... 226 A Process for Making Partially Hydrolyzed Polyacrylamide With High Molecular Weight ...... 226 Process Description ...... 229 Cost Estimate ...... 230 A Process for Making a Mannich Reaction Product of Polyacrylamide 230 Process Descriptio: ...... 230 Cost Estimate ...... 230 Sulfomethylated Poiyac&iaiide'with Medium Molecular 238 Weight ...... Sulfomethyiated Polyacrylamide in Dilute Solution 238
11 COPOLYMERIZATION OF ACRYLAMIDE ...... 245 Review of Products and Processes ...... 245 Kinetics ...... 245 Review of Patents on Copolymers ...... 248 Copolymerization Processes ...... 272 Catalysts for Copolymerization ...... 274 Copolymerization Equipment ...... 274 Recovery of Product ...... 274 Process Evaluations ...... 275 Copolymerization of Acrylamide and Sodium Acrylate in Emulsion ...... 275 CONTENTS
11 COPOLYMERIZATION OF ACRYLAMIDE (Continued) Copolymerization of Acrylamide and Acrylic Acid in the Presence of Salt ...... 275 Copolymerization of Acrylamide, Methacrylic Acid and Maleic Anhydride ...... 278 A Process for Making a Cationic Polyacrylamide Containing Diallyldimethylammonium Chloride ...... 278 A Process for Making a Cationic Polyacrylamide Containing Quaternized Dimethylaminoethyl Methacrylate . . . . . 280 A Process for Making a Cationic Copolymer of Aciyiamide and 2-Methyl-5-Vinylpyridine ...... 281
12 POLYACRYLAMIDE FROM POLYACRYLONITRILE ...... 285 Process Description ...... 285 Process Discussion ...... 290 Cost Estimate ...... 290
13 OTHER PROCESSES FOR MAKING ACRYLAMIDE AND POLYACRYLAMIDE ... 295 Acrylamide ...... 295 From AcryloAi;rili through Hydrochloric Acid Hydrolysis...... 295 From Acrylylchloride ...... 295 From Hydracrylamide or B-Alkoxy-propionamide ...... 295 From 8-Dialkylamino-propionamide ...... 296 From Aldehyde Cyanhydrin ...... 296 From Acrylic Anhydride ...... 296 From Ethylene, Carbon Monoxide and Ammonia ...... 296 By Pyrolysis of Acetoxypropionamide ...... 296 From Alkyl Acrylate ...... 296 Polyacrylamide from Polyacrylate or Polyacrylylchloride ... 296
APPENDIX A DESIGN AND COST BASES ...... 297
APPENDIX B PHYSICAL PROPERTIES OF ACRYLAMIDE AND ACRYLAMIDE SOLUTIONS ...... 299
APPENDIX C PROPERTIES OF POLYACRYLAMIDE ...... 303
APPENDIX D TOXICITY ...... 307
xi CONTENTS
APPENDIX E DISSOLUTION OF POLYACRYLAMIDE ...... 309
APPENDIX F THERMOCHEMICAL DATA ...... 311
CITED REFERENCES ...... 313
PATENTREFERENCES BY COMPANY ...... 359
xii ILLUSTRATIONS
5.1 Manufacture of Acrylamide Comparison of Process Economics ...... 44
5.2 Polymerization of Acrylamide Comparison of Process Economics ...... 47
5.3 Anionic Polyacrylamide Manufacture (27% Hydrolyzed) Comparison of Process Economics ...... 50
6.1 Acrylamide by the Sulfuric Acid Process ...... 375
6.2 Acrylamide by the Sulfuric Acid Process Effect of Operating Level and Plant Capacity on Production Cost ...... 72
7.1 Acrylamide by Hydration of Acrylonitrile Using Fixed Bed Catalyst ...... , ...... 377
7.2 Acrylamide by Hydration of Acrylonitrile Using Fixed Bed Catalyst Effect of Operating Level and Plant Capacity on Production Cost ...... 95
7.3 Acrylamide by Hydration of Acrylonitrile Using Suspended Catalyst ...... , . 379
7.4 Acrylamide by Hydration of Acrylonitrile Using Suspended Catalyst Effect of Operating Level and Plant Capacity on Production Cost ...... 105
7.5 Conversion of 50% Solution to Solid Acrylamide ...... 107
9.1 Polyacrylamide with Medium Molecular Weight by a Solution Process ...... 381
9.2 Polyacrylamide with Medium Molecular Weight by a Solution Process Effect of Operating Level and Plant Capacity on Production Cost ...... 158
9.3 Polyacrylamide with High Molecular Weight by a Solution Process ...... 383
xiii ILLUSTRATIONS
9.4 Polyacrylamide with High Molecular Weight by a Solution Process Effect of Operating Level and Plant Capacity on Production Cost , ...... 166
9.5 Polyacrylamide with Very High Molecular Weight by a Solution Process . . , ...... 385
9.6 Polyacrylamide with Very High Molecular Weight by a Solution Process Effect of Operating Level and Plant Capacity on Production Cost ...... 174
9.7 Polyacrylamide with Extremely High Molecular Weight by a Solution Process ...... 387
9.8 Polyacrylamide with Extremely High Molecular Weight by a Solution Process Effect of Operating Level and Plant Capacity on Production Cost ...... 183
9.9 Polyacrylamide by an Emulsion Process ...... 389
9.10 Polyacrylamide by an Emulsion Process Effect of Operating Level and Plant Capacity on Production Cost ...... 192
9.11 Polyacrylamide by a Precipitation Process ...... 391
9.12 Polyacrylamide by a Precipitation Process Effect of Operating Level and Plant Capacity on Production Cost ...... 200
10.1 Anionic Polyacrylamide by Simultaneous Polymerization and Hydrolysis ...... 393
10.2 Anionic Polyacrylamide by Simultaneous Polymerization and Hydrolysis Effect of Operating Level and Plant Capacity on Production Cost . . . . . , ...... 225
xiv ILLUSTRATIONS
10.3 Partially Hydrolyzed Polyacrylamide with Very High Molecular Weight Effect of Operating Level and Plant Capacity on Production Cost ...... , ...... 228
10.4 Anionic Polyacrylamide with High Molecular Weight ...... 231
10.5 Partially Hydrolyzed Polyacrylamide with High Molecular Weight Effect of Operating Level and Plant Capacity on Production Cost ...... 234
10.6 Cationic Polyacrylamide by Mannich Reaction Effect of Operating Level and Plant Capacity on Production Cost ...... 237
10.7 Sulfomethylated Polyacrylamide Effect of Operating Level and Plant Capacity on Production Cost ...... 241
12.1 Anionic Polyacrylamide from Polyacrylonitrile ...... 395
12.2 Anionic Polyacrylamide from Polyacrylonitrile Effect of Operating Level and Plant Capacity on Production Cost ...... 293
c.1 Viscosity of Polyacrylamide Aqueous Solution ...... 305
xv TABLES
2.1 Cost of Acrylamide Manufacture ...... 5
2.2 Cost of Nonionic Acrylamide Homopolymer Manufacture ...... 10
2.3 Cost of Anionic Polyacrylamide Manufacture by - After-treatment ...... 11
2.4 Cost of Anionic Acrylamide Copolymer Manufacture ...... 13
2.5 Cost of Cationic Polyacrylamide Manufacture ...... 14
3.1 Producers of Acrylamide . . . . . s ...... 20
3.2 Producers of Polyacrylamide ...... 21
3.3 Estimated End-Use Pattern for Polyacrylamides ...... 23
5.1 Comparison of Processes for Polymerization of 0 Acrylamide ...... 45
5.2 Comparison of Processes for Producing Anionic Polyacrylamide ...... 49
6.1 Acrylamide by Sulfuric Acid Process--Hydrolysis and Neutralization Patent Summary ...... 54
6.2 Acrylamide by Sulfuric Acid Process--Purification and Related Operations Patent Summary ...... 58
6.3 Acrylamide by Sulfuric Acid Process Design Bases and Assumptions ...... 64
6.4 Acrylamide by Sulfuric Acid Process Major Process Equipment and Utilities Summary ...... 65
xvii TABLES
6.5 Acrylamide by Sulfuric Acid Process Stream Flows ...... 67
6.6 Acrylamide by Sulfuric Acid Process Total Capital Investment ...... 70
6.7 Acrylamide by Sulfuric Acid Process Production Costs ...... 71
7.1 Acrylamide by Catalytic Hydration of Acrylonitrile Patent Summary ...... 74
7.2 Acrylamide by Catalytic Hydration of Acrylonitrile-- Purification, Concentration and Handling Patent Summary ...... 82
7.3 Acrylamide by Hydration of Acrylonitrile Using Fixed Bed Catalyst Design Bases and Assumptions ...... , . . . . . 87
7.4 Acrylamide by Hydration of Acrylonitrile Using Fixed Bed Catalyst Major Process Equipment and Utilities Suwtary ...... 88
7.5 Acrylamide by Hydration of Acrylonitrile Using Fixed Bed Catalyst Stream Flows ...... 90
7.6 Acrylamide by Hydration of Acrylonitrile Using Fixed Bed Catalyst Total Capital Investment . . . :...... 93
7.7 Acrylamide by Hydration of Acrylonitrile Using Fixed Bed Catalyst Production Costs ...... 94
7.8 Acrylonitrile by Hydration of Acrylonitrile Using Suspended Catalyst Design Bases and Assumptions ...... 97
7 ..9 Acrylamide by Hydration of Acrylonitrile Using Suspended Catalyst Stream Flows ...... 98
xviii - -
TABLES
7.10 Acrylamide by Hydration of Acrylonitrile Using Suspended Catalyst Major Process Equipment and Utilities Summary ...... 99
7.11 Acrylamide by Hydration of Acrylonitrile Using Suspended Catalyst Total Capital Investment ...... 103
7.12 Acrylamide by Hydration of Acrylonitrile Using Suspended Catalyst Production Costs ...... 104
7.13 Conversion of 50% Solution to Solid Acrylamide Stream Flows ...... 108
7.14 Acrylamide by Hydration of Acrylonitrile Using Suspended Catalyst Comparison of Costs for Producing Solution or Solid Acrylamide ...... 108 0- 8.1 Polymerization of Acrylamide in Aqueous Solution Patent Summary ...... 120
8.2 Recovery of Polyacrylamide as Solid from an Aqueous Reaction Product Patent Summary ...... 127
8.3 Means for Improving the Dissolution of Polyacrylamide Patent Summary ...... 129
8.4 Stabilizers for Polyacrylamide Patent Summary ...... 131
8.5 Precipitation Processes for Acrylamide Polymerization Patent Summary ...... 133
8.6 Polymerization of Acrylamide in Suspension of an Organic No-Solvent Liquid Patent Summary ...... 134
8.7 Polymerization of Acrylamide in Oil-in-Water Emulsion Patent Summary ...... 137
xix TABLES
8.8 Polymerization of Acrylamide in Water-in-Oil Emulsion Patent Summary ...... , ...... 138
8.9 Equipment for Polymerization Patent Summary ...... 141
8.10 Photo-Activated Polymerization of Acrylamide Patent Summary ...... 145
8.11 Radiation Polymerization of Acrylamide Patent Sunrnary ...... 147
9.1 Processes for the Manufacture of Polyacrylamide Design Bases and Assumptions ...... 150
9.2 Polyacrylamide with Medium Mol Wt by a Solution Process s Major Process Equipment and Utilities Summary ...... 151
9.3 Polyacrylamide with Medium Mol Wt by a Solution Process Stream Flows ...... 152
9.4 Polyacrylamide with Medium Mol Wt by a Solution Process Total Capital Investment ...... 156
9.5 Polyacrylamide with Medium Mol Wt by a Solution Process Production Costs ...... 157
9.6 Polyacrylamide with High Mol Wt by a Solution Process Major Process Equipment and Utilities Sumnary ...... 159
9.7 Polyacrylamide with High Mol Wt by a Solution Process Stream Flows ...... 160
9.8 Polyacrylamide with High Mol Wt by a Solution Process Total Capital Investment ...... 164
xx TABLES
9.9 Polyacrylamide with High Mol Wt by a Solution Process Production Costs ...... 165
9.10 Polyacrylamide with Very High Mol Wt by a Solution Process Major Process Equipment and Utilities Summary ...... 167
9.11 Polyacrylamide with Very High Mol Wt by a Solution Process Stream Flows ...... 169
9.12 Polyacrylamide with Very High Mol Wt by a Solution Process Total Capital Investment ...... 172
9.13 Polyacrylamide with Very High Mol Wt by a Solution Process Production Costs ...... 173
9.14 Polyacrylamide with Extremely High MoL Wt by a Solution Process Major Process Equipment and Utilities Summary ...... 176
9.15 Polyacrylamide with Extremely High Mol Wt by a Solution Process Stream Flows ...... 178
9.16 Polyacrylamide with Extremely High Mol Wt by a Solution Process Total Capital Investment ...... 181
9.17 Polyacrylamide with Extremely High Mol Wt by a Solution Process Production Costs ...... 182
9.18 Polyacrylamide by an Emulsion Process Major Process Equipment and Utilities Summary ...... 184
9.19 Polyacrylamide by an Emulsion Process Stream Flows ...... 186
9.20 Polyacrylamide by an Emulsion Process Total Capital Investment ...... 190
9.21 Polyacrylamide by an Emulsion Process Production Costs ...... 191
xxi TABLES
9.22 Polyacrylamide by a Precipitation Process Major Process Equipment and Utilities Summary ...... 193
9.23 Polyacrylamide by a Precipitation Process Stream Flows ...... 195
9.24 Polyacrylamide by a Precipitation Process Total Capital Investment ...... 198
9.25 Polyacrylamide by a Precipitation Process Production Costs ...... 199
10.1 Hydrolysis of Polyacrylamide Patent Surmnary ...... 203
10.2 Partially Hydrolyzed Polyacrylamide by Simultaneous Polymerization and Hydrolysis Patent Summary ...... 204
10.3 Methylolation of Polyacrylamide Patent Sunrnary ...... 206
10.4 Sulfomethylation of Polyacrylamide Patent Summary ...... 208
10.5 Cationic Polyacrylamide Derivative by Mannich Reaction Patent Summary ...... 210
10.6 Hoffman Degradation of Polyacrylamide Patent Summary ...... 212
10.7 Various Cationic Polymers Derived from Polyacrylamides Patent Summary ...... 213
10.8 Insolubilization of Polyacrylamide Patent Summary ...... 215
10.9 Grafted Polyacrylamide Patent Summary ...... 217
10.10 Other Polyacrylamide Derivatives Patent Summary ...... 218
xxii -
TABLES
10.11 Evaluation of Several Polyacrylamide Derivatives 0 Design Bases and Assumptions ...... 219
10.12 Anionic Polyacrylamide by Simultaneous Polymerization and Hydrolysis Major Process Equipment and Utilities Summary ...... 220
10.13 Anionic Polyacrylamide by Simultaneous Polymerization and Hydrolysis Stream Flows ...... 221
10.14 Anionic Polyacrylamide by Simultaneous Polymerization and Hydrolysis Total Capital Investment ...... 223
10.15 Anionic Polyacrylamide by Simultaneous Polymerization and Hydrolysis Production Costs ...... 224
10.16 Partially Hydrolyzed Polyacrylamide with Very High Molecular Weight Production Costs ...... 227
10.17 Partially Hydrolyzed Polyacrylamide with High Molecular Weight Total Capital Investment ...... 232
10.18 Partially Hydrolyzed Polyacrylamide with High Molecular Weight Production Costs ...... 233
10.19 Mannich Reaction Product of Polyacrylamide Total Capital Investment ...... 235 0 10.20 Mannich Reaction Product of Polyacrylamide Production Costs ...... 236
10.21 Sulfomethylated Polyacrylamide with Medium Molecular Weight (Solid) Total Capital Investment ...... 239
10.22 Sulfomethylated Polyacrylamide with Medium Molecular Weight (Solid) Production Costs ...... 240
. . . xx111 TABLES
10.23 Sulfomethylated Polyacrylamide Produced at Site Total Capital Investment ...... 243
10.24 Sulfomethylated Polyacrylamide Produced at Site Production Costs ...... 244
11.1 Reactivity Ratios of Monomers in Copolymerization . . . . . 246
11.2 Copolymers of Acrylamide and Acrylic Acid or Acrylate Patent Summary ...... 249
11.3 Cationic Polyacrylamide from Acrylamide and (Metha)AcryLic Derivatives Patent Sunrnary ...... 251
11.4 Copolymers of Acrylamide and (Metha)Acrylic Esters Patent Summary ...... 252
11.5 Copolymers of Acrylamide and Other Unsaturated Amides Patent Sunrnary ...... 254
11.6 Copolymers of Acrylamide and Diallyl Compounds Patent Summary ...... 258
11.7 Copolymers of Acrylamide and Dibasic Unsaturated Acids Patent Summary ...... 259
11.8 Copolymers of Acrylamide and Styrene Patent Summary ...... 260
11.9 Copolymers of Acrylamide and N-substituted Lactams Patent Summary ...... 261
11.10 Copolymers of Acrylamide and Acrylonitrile Patent Summary ...... 262
11.11 Copolymers of Acrylamide and Acrolein Patent Summary ...... 263
11.12 Copolymers of Acrylamide and Olefins Patent Summary ...... 264
xxiv TABLES
11.13 Copolymers of Acrylamide and Vinyl Esters Patent Summary ...... 265
11.14 Copolymers of Acrylamide and Sulfur--Containing Compounds Patent Sunxnary ...... , ...... 266
- 11.15 Silicon-Containing Polyacrylamide Patent Summary ...... 267
11.16 Phosphorus-ContainingAcrylamide Copolymers Patent Summary ...... 268
11.17 Acrylamide Grafted on Starch Patent Summary ...... 269
11.18 Acrylamide Grafted on Polymers Patent Summary ...... 270
11.19 Miscellaneous Copolymers Containing Acrylamide 0 Patent Summary ...... 271 11.20 Anionic Copolymers of Acrylamide and Acrylic Acid Design Bases and Assumptions ...... 276
11.21 Anionic Copolymers of Acrylamide and Acrylic Acid Cost Estimates ...... 277
11.22 Cationic Polyacrylamides Design Bases and Assumptions ...... 279
11.23 Cationic Polyacrylamides Cost Estimates ...... 282
12.1 Anionic Copolymer Via Polyacrylonitrile Design Bases and Assumptions ...... 286
12.2 Anionic Copolymer Via Polyacrylonitrile Major Process Equipment and Utilities Swmnary . , . . . . . 287
12.3 Anionic Copolymer Via Polyacrylonitrile - Stream Flows ...... 289
l xxv TABLES
12.4 Anionic Copolymer Via Polyacrylonitrile Total Capital Investment ...... 291
12.5 Anionic Copolymer Via Polyacrylonitrile Production Costs , . . . , , , ...... 292 l
xxvi