process economics program - · pdf filep- and o-nitrochlorobenzene from chlorobenzene ........
TRANSCRIPT
PROCESS ECONOMICS
PROGRAM
l ABSTRACT
Process Economics Program Report No. 171A
(August 1985)
SRI INTERNATIONAL
Menlo Park, California
94025
-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.
0
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
another from ethylene oxide are evaluated and compared.
PEP'84 YCY, DJL, CSL
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Report No.171A
PESTICIDES AND INTERMEDIATES
SUPPLEMENT A
by YEN-CHEN YEN
with contributions by DIN-JIN LIN
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 CHEMICAL ECONOMICS HANDBOOK Program covers
most major chemicals and chemical products produced in the
United States and the WORLD PETROCHEMICALS Program covers
major hydrocarbons and their derivatives on a worldwide basis.
In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company, prod-
uct, and plant for the United States and Western Europe.
ii
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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 ........................
Chemistry ........................ The Catechol Route to Producing the Benzofuran Derivative The o-Nitrophenol Route to Producing the Renzofuran Derivative ....................... Review of Processes ................... A Process for Making Carbofuran from Catechol ......
Process Description .................. Process Discussion ................... Cost Estimates. ....................
A Process for Making Carbofuran from o-Nitrochlorobenzene via o-Nitrophenol .................... Process Description ..................
iii
. 37
. 37 . 38
. 39
. 48
. 57
. 57
. 68
. 70
. 74
. 74
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 . . . . . . . . . . . . . . . . . . . Process Discussion . . . . . . . . . . . . . . . . . . . . Cost Estimates . . . . . . . . . . . . . . . . . . . . . .
Use of
APPENDIX A
APPENDIX B
APPENDIX c
APPENDIX D
APPENDIX E
APPENDIX F
Hydrocarbons Other than Natural Gas .........
PROPERTIES OF CARBOFURAN ..............
SOME PHYSICAL PROPERTIES OF INTERMEDIATES IN CARBOFURAN PREPARATION ...............
TOXICITY OF METHYL ISOCYANATE ...........
PROPERTIES OF MANCOZEB ...............
TOXICITY AND HAZARD OF CARBON DISULFIDE ......
DATA ON HEATS OF REACTION .............
CITEDREFERENCES ........................
PATENT REFERENCES. .......................
305 312 313 314
319
321
323
325
327
329
333
349
vi
ILLUSTRATIONS
4.1 Carbofuran from Catechol
4.2
4.3
5.1
Plowsheet........................ 355
Carbofuran from o-Nitrochlorobenzene Flowsheet........................ 361
Carbofuran from Benzofuran Flowsheet........................ 367
Methyl Isocyanate from Methylamine via Esterification and Splitting
Flowsheet........................ 369
Methyl Isocyanate Production FlowSheet........ . . . . . . . . . . . . . . . . 371
Methyl Isocyanate via Diphenyl Carbonate FlowSheet.. . . . . . . . . . . . . . . . . . . . . . . 373
Methyl Isocyanate via N-methylformamide Flowsheet........................ 377
Methallyl Chloride from Isobutylene Flowsheet........................ 379
Catechol from Phenol by Hydroxylation FlowSheet.. . . . . . . . . . . . . . . . . . . . . . . 381
Sensitivity of the Product Value of Catechol to the Prices of Phenol and Hydrogen Peroxide . . . . . . . . . 207
Production of o- and p-Nitrochlorobenzenes FlowSheet.. . . . . . . . . . . . . . . . . . . . . . . 385
The Relationship of the Product Value of the p-Isomer to Credit for o-Isomer . . . . . . . . . . . . . . . . . . . 228
Mancozeb Manufacture FlowSheet.. . . . . . . . . . . . . . . . . . . . . . . 389
Ethyleneamines from Ethylene Dichloride Flowsheet........................ 391
Ethylenediamines from Ethylene Oxide Flowsheet........................ 393
Carbon Disulfide from Natural Gas Flowsheet........................ 397
5.2
5.3
5.4
6.1
7.1
7.2
8.1
8.2
9.1
10.1
10.2
11.1
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
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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
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
3.10 World Producers of Ethyleneamines, 1984 . . . . . . . . . 34
3.11 World Producers of Carbon Disulfide, 1984 . . . . . . . . 35
4.1 Carbamate Insecticides . . . . . . . . . . . . . . . . . 40
4.2 Carbofuran Patent Summary . . . . . . . . . . . . . . . . . . . . . 50
4.3 Carbofuran from Catechol 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
4.16 Carbofuran from o-Nitrochlorobenzene Production Costs . . . . . . . . . . . . . . . . . . . . 101
4.17 Comparison of the Catechol and o-Nitrochlorobenzene Routes to Carbofuran . . . . . . . . . . . . . . . . . . 105
4.18 Carbofuran Manufacture Without Using Methyl Isocyanate Design Bases and Assumptions . . . . . . . . . . . . . . 107
X
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TABLES
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4.19 Carbofuran from Benzofuran, Phosgene, and Methylamine Stream Flows . . . . . . . . . . . . . . . . . . . . . . 108
4.20 Carbofuran from Benzofuran, Phosgene, and Methylamine Major Equipment. . . . . . . . . . . . . . . . . . . . . 110
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
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
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5.24
6.1
6.2 Methallyl Chloride from Isobutylene . . . . . . . . . . . 183
6.3 Methallyl Chloride from Isobutylene Stream Flows . . . . . . . . . . . . . . . . . . . . . . 184
6.4
6.5
6.6
6.7
7.1
7.2
7.3
7.4
7.5
7.6
8.1
Other Processes for Making Methyl Isocyanate Patent Summary . . . . . . . . . . . . . . . . . . . . . 176
Methallyl Chloride Preparation Patent Summary . . . . . . . . . . . . . . . . . . . . . 180
Fiethallyl Chloride from Isobutylene Major Equipment. . . . . . . . . . . . . . . . . . . . . 185
Methallyl Chloride from Isobutylene Utilities Summary . . . . . . . . . . . . . . . . . . . . 186
Methallyl Chloride from Isobutylene Total Capital Investment . . . . . . . . . . . . . . . . 188
Methallyl Chloride from Isobutylene Production Costs . . . . . . . . . . . . . . . . . . . . 189
Catechol Production Using Hydrogen Peroxide Patent Summary . . . . . . . . . . . . . . . . . . . . . 193
Catechol Production Using Peracid Patent Summary . . . . . . . . . . . . . . . . . . . . . 194
Procedures for Separation and Purification of Catechol Hydroquinone Patent Summary . . . . . . . . . . . . . . . . . . . . . 195
Other Processes for Producing Catechol Patent Summary . . . . . . . . . . . . . . . . . . . . . 196
Catechol from Phenol by Hydroxylation Total Capital Investment . . . . . . . . . . . . . . . . 203
Catechol from Phenol by Hydroxylation Production Costs . . . . . . . . . . . . . . . . . . . . 205
Preparation of o-Nitrophenol Patent Summary . . . . . . . . . . . . . . . . . . . . . 210
Xiii
TABLES
0.2
8.3
8.4
8.5
8.6
8.7
9.1
9.2
9.3
9.4
Manufacture of o- and p-Nitrochlorobenzenes Design Bases and Assumptions . . . . . . . . . . . . . . 213
Manufacture of Nitrochlorobeneene Stream Flows . . . . . . . . . . . . . . . . . . . . . . 217
p-Nitrochlorobenzene from Chlorobenzene Major Equipment. . . . . . . . . . . . . . . . . . . . . 218
p-Nitrochlorobenzene from Chlorobenzene Utilities Summary . . . . . . . . . . . . . . . . . . . . 220
p-Nitrochlorobenzene from Chlorobenzene Total Capital Investment . . . . . . . . . . . . . . . . 224
p-Nitrochlorobenzene from Chlorobenzene Production Costs . . . . . . . . . . . . . . . . . . . . 226
Mancozeb, Maneb, and Zineb Patent Summary . . . . . . . . . . . . . . . . . . . . . 231
Other Bisthiocarbamate Fungicides Patent Summary . . . . . . . . . . . . . . . . . . . . . 235
Mancozeb Production Design Bases and Assumptions . . . . . . . . . . . . . . 239
Mancozeb Production StreamFlows . . . . . . . . . . . . . . . . . . . . . . 241
9.5 Mancozeb Production Major Equipment.... . . . . . . . . . . . . . . . . . 244
9.6 Mancozeb Production Utilities Summary . . . . . . . . . . . . . . . . . . . . 245
9.7 Mancozeb Production Total Capital Investment . . . . . . . . . . . . . . . . 248
9.8 Mancozeb Production Production Costs . . . . . . . . . . . . . . . . . . . . 250
9.9 Main Raw Materials Costs for Commercial Mancozeb, Maneb, andzineb . . . . . . . . . . . . . . . . . . . . . . . 252
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10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8
10.9
10.10
10.11
10.12
10.13
10.15
TABLES
Ethyleneamine Processes Patent Summary . . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Dichloride Design Bases and Assumptions . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Dichloride Stream Flows . . . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Dichloride Major Equipment. . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Dichloride Utilities Summary . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Dichloride Total Capital Investment . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Dichloride Production Costs . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from EDC (Without Using Extraction) Production Costs . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Oxide Design Bases and Assumptions . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Oxide Stream Flows . . . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Oxide Major Equipment.... . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Oxide Utilities Summary . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Oxide Total Capital Investment . . . . . . . . . . . . . . . .
Ethyleneamines from Ethylene Oxide Production Costs . . . . . . . . . . . . . . . . . . . .
Ethyleneamines from Monoethanolamine Production Costs . . . . . . . . . . . . . . . . . . . .
xv
254
257
260
262
264
267
270
273
277
278
282
284
286
289
293
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