PROCESS ECONOMICS PROGRAM
SRI INTERNATIONAL
Menlo Park, California ABSTRACT 94025 l Process Economics Program Report No. 171A (August 1985)
-0 This report describes and evaluates the processes for making carbo- furan and mancozeb, as well as the intermediates for these two pesti- cides.
Carbofuran is made from either catechol or o-nitrochlorobenzene. The economics of each route, including the manufacture of the inter- mediates methyl isocyanate and methallyl chloride, are evaluated. The catechol route is found to be economically superior. For methyl iso- cyanate, which is common to both routes, two nonphosgenation processes are evaluated and compared with two phosgenation processes. The non- phosgenation route is not only competitive with the phosgenation route, but also avoids the transport of both methyl isocyanate and Phosgene when integrated with carbofuran production.
Mancoxeb is evaluated in detail, with a brief evaluation of two similar pesticides, maneb, and zineb. The intermediates are carbon disulfide and ethylenediamine. The process for making carbon disulfide from methane and sulfur is evaluated, with a discussion of the use of alternative carbon sources. For ethylenediamine, two processes start- ing from ethylene dichloride, one process from monoethanolamine, and 0 another from ethylene oxide are evaluated and compared.
PEP'84 YCY, DJL, CSL - Report No.171A
0 PESTICIDES AND INTERMEDIATES
SUPPLEMENT A
by YEN-CHEN YEN
with contributions by DIN-JIN LIN 0 and CHUN-SAN LIU
August 1985
A private report by the PROCESS ECONOMICS PROGRAM
Menlo Park, California 94025 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICALECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLDPETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORYOF CHEMICALPRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe.
a
0
ii CONTENTS
1 INTRODUCTION...... 1
2 SUMMARY...... 3 General Aspects ...... 3 Technical Features ...... 13 Carbofuran from Catechol ...... 13 Carbofuran from o-Nitrochlorobenzene ...... 13 Carbofuran Production Without Using Methyl Isocyanate . . 14 Methyl Isocyanate from Methyl Amine Phosgenation ..... 15 Methyl Isocyanate via Diphenyl Carbonate ...... 15 Methyl Isocyanate via N-Methylformamide ...... 15 Methallyl Chloride from the Chlorination of Isobutane . . 16 Catechol and Hydroquinone from Phenol ...... 16 p- and o-Nitrochlorobenzene from Chlorobenzene ...... 16 Mancozeb from Ethylenediamine and Carbon Disulfide .... 17 Ethyleneamines from Ethylene Dichloride byEztractionRecovery ...... 18 Ethyleneamines from Ethylene Dichloride by Evaporation Recovery ...... 18 Ethyleneamines from Monoethanolamine ...... 18 Ethyleneamines from Ethanolamine Starting from Ethylene Oxide ...... 18 Carbon Disulfide from Natural Gas ...... 19
3 INDUSTRYSTATUS ...... 21 Carbofuran...... 21 Intermediates for Carbofuran ...... 23 Mancozeb, Maneb, and Zineb ...... 24 Intermediates for Mancozeb, Maneb, and Zineb ...... 25
4 CARROFURAN ...... 37 Chemistry ...... 37 The Catechol Route to Producing the Benzofuran Derivative . 38 The o-Nitrophenol Route to Producing the Renzofuran Derivative ...... 39 Review of Processes ...... 48 A Process for Making Carbofuran from Catechol ...... 57 Process Description ...... 57 Process Discussion ...... 68 Cost Estimates...... 70 A Process for Making Carbofuran from o-Nitrochlorobenzene via o-Nitrophenol ...... 74 Process Description ...... 74
iii CONTENTS
4 CARROFURAR (continued) Process Discussion ...... Cost Estimates...... Comparison of the Two Processes for Making Carbofuran ... 103 Carbofuran Production Without Methyl Isocyanate ...... 104 Process Description ...... 106 Process Discussion ...... 112 Cost Estimates...... 112 Integration with Isocyanate Production ...... 116
5 METHYL ISOCYANATE ...... 117 Phosgenation of Methylamine ...... 117 Chemistry and Review of Process ...... 117 Process Description ...... 119 Process Discussion ...... 128 Cost Estimates ...... 129 Other Phosgenation Processes ...... 137 A Process for Raking Methyl Isocyanate via Diphenylcarbonate ...... 141 Chemistry and Review of Process ...... 141 Process Description ...... 143 Process Discussion ...... 151 Cost Estimates ...... 151 A Process for Raking Methyl Isocyanate via N-methylformamide ...... 157 Chemistry and Review of Process ...... 157 Process Description ...... 161 Process Discussion ...... 169 Cost Estimates ...... 169 Summary of Evaluation ...... 174
6 MRTUALLYL CHLORIDE ...... 177 Chemistry ...... 177 Review of Processes ...... 178 Process Description ...... 182 Process Discussion ...... 187 Cost Estimates ...... 187
7 CATECHOL...... 191 Review of Processes ...... 191 Hydrolysis of o-Chlorophenol or o-Dichlorobenzene . . . . . 192
IV CONTENTS
7 CATECHOL (continued) Evaluation of a Hydroxylation Process for Making Catechol and Hydroquinone Using Hydrogen Peroxide ...... 197
8 o-NITROPHENOL and o-NITROCULOROBENZENE ...... 209 o-Nitrophenol ...... 209 o-Nitrochlorobenzene ...... 211 Evaluation of a Process for Making Nitrochlorobenzenes ... 212 Process Description ...... 212 Process Discussion ...... 221 Cost Estimates ...... 223
9 MABCOZEB ...... 229 Chemistry ...... 229 Review of Processes ...... 230 Process Description ...... 238 Process Discussion ...... 246 Cost Estimates...... 246
10 ETBYLENEDIAMINE ...... 253 A Process for Producing Ethyleneamines from Ethylene Dichloride Involving Extraction Recovery . . . . . 253 Process Description ...... 253 Process Discussion ...... 265 Cost Estimates ...... 265 Updating of the EDC Process for Baking Ethyleneamines InPEP Report138...... 272 A Process for Producing Ethyleneamines from Ethylene Oxide via Monoethanolamine ...... 275 Process Description ...... 275 Process Discussion ...... 285 Cost Estimates ...... 285 Updating of the Process for Baking Ethyleneamines from Ethanolamine Evaluated in PEP Report 138 ...... 291
11 CARBON DISULFIDE ...... 295 Chemistry ...... 295 Review of Processes ...... 297 Carbon-Sulfur Process ...... 297 Hydrocarbon-Sulfur Process ...... 298 Evaluation of a Process for Making Carbon Disulfide fromNatural Gas ...... 305
V CONTENTS
11 CARBON DISULFIDE (continued) Process Description ...... 305 Process Discussion ...... 312 Cost Estimates ...... 313 Use of Hydrocarbons Other than Natural Gas ...... 314
APPENDIX A PROPERTIES OF CARBOFURAN ...... 319
APPENDIX B SOME PHYSICAL PROPERTIES OF INTERMEDIATES IN CARBOFURAN PREPARATION ...... 321
APPENDIX c TOXICITY OF METHYL ISOCYANATE ...... 323
APPENDIX D PROPERTIES OF MANCOZEB ...... 325
APPENDIX E TOXICITY AND HAZARD OF CARBON DISULFIDE ...... 327
APPENDIX F DATA ON HEATS OF REACTION ...... 329
CITEDREFERENCES ...... 333
PATENT REFERENCES...... 349
vi ILLUSTRATIONS
4.1 Carbofuran from Catechol Plowsheet...... 355 4.2 Carbofuran from o-Nitrochlorobenzene Flowsheet...... 361 4.3 Carbofuran from Benzofuran Flowsheet...... 367 5.1 Methyl Isocyanate from Methylamine via Esterification and Splitting Flowsheet...... 369 5.2 Methyl Isocyanate Production FlowSheet...... 371 5.3 Methyl Isocyanate via Diphenyl Carbonate FlowSheet...... 373 5.4 Methyl Isocyanate via N-methylformamide Flowsheet...... 377 6.1 Methallyl Chloride from Isobutylene Flowsheet...... 379 7.1 Catechol from Phenol by Hydroxylation FlowSheet...... 381 7.2 Sensitivity of the Product Value of Catechol to the Prices of Phenol and Hydrogen Peroxide ...... 207 8.1 Production of o- and p-Nitrochlorobenzenes FlowSheet...... 385 8.2 The Relationship of the Product Value of the p-Isomer to Credit for o-Isomer ...... 228 9.1 Mancozeb Manufacture FlowSheet...... 389 10.1 Ethyleneamines from Ethylene Dichloride Flowsheet...... 391 10.2 Ethylenediamines from Ethylene Oxide Flowsheet...... 393 11.1 Carbon Disulfide from Natural Gas Flowsheet...... 397
Vii TABLES
2.1 Cost Features of Carbofuran Production ...... 4
2.2 Cost Features of Methyl Isocyanate Production ...... 5
2.3 Cost Features of Methallyl Chloride Production . . . . . 7 - 2.4 Cost Features of Catechol Production ...... 8 2.5 Cost Features of p-Nitrochlorobenzene ...... 9
2.6 Cost Features of Mancozeb Production ...... 10
2.7 Cost Features of Ethyleneamines Production ...... 11
2.8 Cost Features of Carbon Disulfide Production ...... 12
3.1 World Producers of Carbofuran, 1984 ...... 22
3.2 World Producers of o-Nitrophenol, 1984 ...... 25
0 3.3 World Producers of p- and o-Nitrochlorobenzene,1984 . . 26
3.4 World Producers of Catechol and Hydroquinone, 1984 . . . 27
3.5 World Producers of Methyl Isocyanate, 1984 ...... 28
3.6 World Producers of Phosgene, 1984 ...... 29
3.7 World Producers of Methylamines, 1984 ...... 31
3.8 World Producers of Methallyl Chloride, 1984 ...... 32
3.9 World Producers of Mancozeb, Maneb, and Zineb, 1984 . . . 33
0 3.10 World Producers of Ethyleneamines, 1984 ...... 34
3.11 World Producers of Carbon Disulfide, 1984 ...... 35
4.1 Carbamate Insecticides ...... 40 a 4.2 Carbofuran Patent Summary ...... 50
4.3 Carbofuran from Catechol 0 Design Bases and Assumptions ...... 60 iX TABLES
4.4 Carbofuran from Catechol Stream Flows ...... 61
4.5 Carbofuran from Catechol Major Equipment ...... 65
4.6 Carbofuran from Catechol Utilities Summary ...... 68
4.7 Carbofuran from Catechol Waste Streams ...... 69
4.8 Carbofuran from Catechol Total Capital Investment ...... 71
4.9 Carbofuran from Catechol Production Costs ...... 72
4.10 Carbofuran from o-Nitrochlorobenzene Design Bases and Assumptions ...... 75
4.11 Carbofuran from o-Nitrochlorobenzene Stream Flows ...... 79
4.12 Carbofuran from o-Nitrochlorobenzene Major Equipment...... 90
4.13 Carbofuran from o-Nitrochlorobenzene Utilities Summary ...... 94
4.14 Carbofuran from o-Nitrochlorobenzene Waste Streams ...... 96
4.15 Carbofuran from o-Nitrochlorobenzene Total Capital Investment ...... 98 a
4.16 Carbofuran from o-Nitrochlorobenzene Production Costs ...... 101
4.17 Comparison of the Catechol and o-Nitrochlorobenzene Routes to Carbofuran ...... 105 a
4.18 Carbofuran Manufacture Without Using Methyl Isocyanate Design Bases and Assumptions ...... 107 a X TABLES
- 4.19 Carbofuran from Benzofuran, Phosgene, and Methylamine Stream Flows ...... 108
4.20 Carbofuran from Benzofuran, Phosgene, and Methylamine Major Equipment...... 110 0 4.21 Carbofuran from Benzofuran, Phosgene, and Methylamine Utilities Summary ...... 111
4.22 Carbofuran from Benzofuran, Phosgene, and Methylamine Total Capital Investment ...... 114
4.23 Carbofuran from Catechol Without Using Methyl Isocyanate Production Costs ...... 115
5.1 Methyl Isocyanate Preparation by Phosgenation of Methylamine Patent Summary ...... 118
5.2 Methyl Isocyanate from Methylamine Design Bases and Assumptions ...... 120
5.3 Methyl Isocyanate from Methylamine via Esterification and Splitting Stream Flows ...... 123
5.4 Methyl Isocyanate from Methylamine via Esterification and Splitting Major Equipment ...... 126
5.5 Methyl Isocyanate from Methylamine via Esterification and Splitting Utilities Summary ...... 128
5.6 Methyl Isocyanate from Methylamine via Esterification and Splitting Total Capital Investment ...... 131
5.7 Methyl Isocyanate from Methylamine via Esterification and Splitting - Production Costs ...... 133
5.8 Methyl Isocyanate from Ethylamine via Esterification Splitting (Anhydrous HCl) Production Costs ...... 135 0 xi TABLES
5.9 Methyl Isocyanate Through Carbamyl Chloride Decomposition Production Costs ...... 139
5.10 Methyl Isocyanate via Diphenyl Carbonate Patent Summary ...... 142
5.11 Methyl Isocyanate via Diphenyl Carbonate Design Bases and Assumptions ...... 144
5.12 Methyl Isocyanate via Diphenyl Carbonate Stream Flows ...... 145
5.13 Methyl Isocyanate via Diphenyl Carbonate Major Equipment ...... 149
5.14 Methyl Isocyanate via Diphenyl Carbonate Utilities Summary ...... 150
5.15 Methyl Lsocyanate via Diphenyl Carbonate Total Capital Investment ...... 153
5.16 Methyl Isocyanate via Diphenyl Carbonate Production Costs ...... 155
5.17 Methyl Isocyanate Preparation via N-Methylformamide Patent Summary ...... 159
5.18 Methyl Isocyanate via Ethylene Carbonate and Urethane Design Bases and Assumptions ...... 162
5.19 Methyl Isocyanate via N-Methylformamide StreamFlows ...... 164
5.20 Methyl Isocyanate via N-Methylformamide Major Equipment...... 166
5.21 Methyl Isocyanate via N-Methylformamide Utilities Summary ...... 168
5.22 Methyl Isocyanate via N-Methylformamide Total Capital Investment ...... 170
5.23 Methyl Isocyanate via N-Methylformamide Production Costs ...... 172
Xii TABLES
5.24 Other Processes for Making Methyl Isocyanate Patent Summary ...... 176
6.1 Methallyl Chloride Preparation Patent Summary ...... 180
6.2 Methallyl Chloride from Isobutylene ...... 183
6.3 Methallyl Chloride from Isobutylene Stream Flows ...... 184
6.4 FiethallylChloride from Isobutylene Major Equipment...... 185
6.5 Methallyl Chloride from Isobutylene Utilities Summary ...... 186
6.6 Methallyl Chloride from Isobutylene Total Capital Investment ...... 188
6.7 Methallyl Chloride from Isobutylene Production Costs ...... 189
7.1 Catechol Production Using Hydrogen Peroxide Patent Summary ...... 193
7.2 Catechol Production Using Peracid Patent Summary ...... 194
7.3 Procedures for Separation and Purification of Catechol Hydroquinone Patent Summary ...... 195
7.4 Other Processes for Producing Catechol Patent Summary ...... 196
7.5 Catechol from Phenol by Hydroxylation Total Capital Investment ...... 203
7.6 Catechol from Phenol by Hydroxylation - Production Costs ...... 205
8.1 Preparation of o-Nitrophenol Patent Summary ...... 210 a Xiii TABLES
0.2 Manufacture of o- and p-Nitrochlorobenzenes Design Bases and Assumptions ...... 213
8.3 Manufacture of Nitrochlorobeneene Stream Flows ...... 217
8.4 p-Nitrochlorobenzene from Chlorobenzene Major Equipment...... 218
8.5 p-Nitrochlorobenzene from Chlorobenzene Utilities Summary ...... 220
8.6 p-Nitrochlorobenzene from Chlorobenzene Total Capital Investment ...... 224
8.7 p-Nitrochlorobenzene from Chlorobenzene Production Costs ...... 226
9.1 Mancozeb, Maneb, and Zineb Patent Summary ...... 231
9.2 Other Bisthiocarbamate Fungicides Patent Summary ...... 235
9.3 Mancozeb Production Design Bases and Assumptions ...... 239
9.4 Mancozeb Production StreamFlows ...... 241
9.5 Mancozeb Production Major Equipment...... 244
9.6 Mancozeb Production 0 Utilities Summary ...... 245
9.7 Mancozeb Production Total Capital Investment ...... 248
9.8 Mancozeb Production 0 Production Costs ...... 250
9.9 Main Raw Materials Costs for Commercial Mancozeb, Maneb, andzineb ...... 252 a Xiv TABLES
10.1 Ethyleneamine Processes Patent Summary ...... 254
10.2 Ethyleneamines from Ethylene Dichloride Design Bases and Assumptions ...... 257
10.3 Ethyleneamines from Ethylene Dichloride Stream Flows ...... 260
10.4 Ethyleneamines from Ethylene Dichloride Major Equipment...... 262
10.5 Ethyleneamines from Ethylene Dichloride Utilities Summary ...... 264
10.6 Ethyleneamines from Ethylene Dichloride Total Capital Investment ...... 267
10.7 Ethyleneamines from Ethylene Dichloride Production Costs ...... 270
10.8 Ethyleneamines from EDC (Without Using Extraction) Production Costs ...... 273
10.9 Ethyleneamines from Ethylene Oxide Design Bases and Assumptions ...... 277
10.10 Ethyleneamines from Ethylene Oxide Stream Flows ...... 278
10.11 Ethyleneamines from Ethylene Oxide Major Equipment...... 282
10.12 Ethyleneamines from Ethylene Oxide Utilities Summary ...... 284
10.13 Ethyleneamines from Ethylene Oxide Total Capital Investment ...... 286
Ethyleneamines from Ethylene Oxide Production Costs ...... 289
10.15 Ethyleneamines from Monoethanolamine Production Costs ...... 293
xv TABLES
11.1 Carbon Disulfide from Methane or Other Hydrocarbons Patent Summary ...... 300
11.2 Carbon Disulfide from Natural Gas Design Bases and Assumptions ...... 306
11.3 Carbon Disulfide from Natural Gas Stream Flows ...... 308
11.4 Carbon Disulfide from Natural Gas Major Equipment...... 310
11.5 Carbon Disulfide from Natural Gas Utilities Summary ...... 312
11.6 Carbon Disulfide from Natural Gas Total Capital Investment ...... 315
11.7 Carbon Disulfide from Natural Gas Production Costs ...... 317