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Report No. 77
ACETONE, METHYL ETHYL KETONE AND
METHYL ISOBUTYL KETONE
by SHIGEYOSHI TAKAOKA
May 1972
A private report by the
PROCESS ECONOMICS PROGRAM
I STANFORD RESEARCH INSTITUTE
I MENLO PARK, CALIFORNIA
a CONTENTS
1 INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . 1
2 SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Acetone .......................... 3 Methyl Ethyl Ketone .................... 6 Methyl Isobutyl Ketone ................... 11
3 INDUSTRY STATUS . . . . . . . . . . . . , . , . . . . . . , 15
Acetone .......................... 15 Methyl Ethyl Ketone .................... 20 Secondary Butanol ..................... 21 Methyl Isobutyl Ketone ................... 22 Diacetone Alcohol ..................... 25 Mesityl Oxide ....................... 26
4 ACETONE BY DERYDROGERATION OF ISOPROPANOL ......... 27
Chemistry ......................... 27 Mechanism ........................ 27 Kinetics ......................... 28
Review of Processes .................... 30 Feed Specifications ................... 31 Catalyst ......................... 31 Reactor ......................... 38 Temperature and Pressure ................. 38 Space Velocity ...................... 38 Conversion, Selectivity, and Yield ............ 39 By-products ....................... 39 Product Purification ................... 39
Process Description .................... 40 Process Discussion ..................... 46 Cost Estimates ....................... 48 Capital Costs ...................... 48 Production Costs ..................... 49
5 ACETONE BY DIRECT OXIDATION OF PROPYLENE .......... 59
Chemistry ......................... 59 Review of'Processes .................... 64 Feed Specifications ................... 71 Catalyst ......................... 71 Reactor ......................... 72
V
CONTENTS
5 (continued)
Temperature and Pressure ................. 73 Conversion, Selectivity, and Yield ............ 73 By-products ....................... 74
Product Purification ................... 74 Material of Construction ................. 75 Other Propylene Oxidation Processes ........... 76
Process Description .................... 76 Process Discussion .................... 83 Cost Estimates ....................... 86 Capital Costs ...................... 86 Production Costs ..................... 86
6 ACETONE BY OTHER PROCESSES ................. 93
Cumene Hydroperoxide Process ................ 93 Oxidation of Isopropanol .................. 94 Reaction of Acetylene and Steam .............. 95
Oxidation of Light Paraffinic Hydrocarbons ......... 96 Ketonization of Acetic Acid ................ 96 Reaction of Acetaldehyde and Steam ............. 97
Reaction of Propylene and Acetic Acid ........... 97 Isomerization of Propylene Oxide .............. 98 Various Other Processes .................. 98
7 SECONDARY BUTANOL BY SULFATION AND HYDROLYSIS OF NORMAL BUTYLENES ......................... 101
Chemistry ......................... 101
Review of Processes .................... 102 Sulfation ........................ 102 Hydrolysis ........................ 104 Purification ....................... 104
Process Description .................... 106 Process Discussion ..................... 114 Cost Estimates ....................... 118 Capital Costs ...................... 118 Production Costs ..................... 118
vi
CONTENTS
8 METHYL ETHYL KETONE BY DEHYDROGENATION OF SECONDARY BUTANOL . . . . . . . . . . . . . . . . . . . . . .
Chemistry ..................... Review of Processes ................ Feed Specifications ............... Catalyst ..................... Reactor ..................... Temperature and Pressure ............. Space Velocity .................. Conversion, Selectivity, and Yield ........ By-products ................... Product Purification ...............
Process Description ................ Process Discussion ................. Cost Estimates ................... Capital Costs .................. Production Costs .................
9 METHYL ETHYL KETONE BY DIRECT OXIDATION OF NORMAL BUTYLENES .....................
Chemistry ..................... Review of Processes ................ Feed Specifications ............... Catalyst ..................... Temperature and Pressure ............. Conversion, Selectivity, and Yield ........ 'By-products ................... Product Purification ............... Material of Construction .............
Process Description ................ Process Discussion ................. Cost Estimates ................... Capital Costs .................. Production Costs .................
. 10 METHYL ETHYL KETONE BY OTHER PROCESSES . . . . . . . . . . . 189
Oxidation of Light Hydrocarbons . . . . . . . . . . . . . . 189 set-Butylbenzene Hydroperoxide Process . . . . , . . . . . . 190 Oxidation of set-Butanol . . . . . . . . . . . . . . . . . . 190 Isomerization of Butylene Oxide . . . . . . . . . . . . . . 191 Isomerization of Isobutyl Aldehyde . . . , . . . . . . . . . 191 Electrochemical Oxidation of n-Butylenes . . . . . . . . . . 191 Various Other Processes . . . . . . . . . . . . . . . . . , 192
Vii
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. . . . 165 , . . . 165 . . . . 165 . . . . 166 . . . . 167 . . . . 167 . . . , 179 . . . . 181 . . . . 181 . . . , 182
CONTENTS
11 METHYL ISOBUTYL KETONE FROM ACETONE VIA MESITYL OXIDE . . . 193
Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . 193 Condensation of Acetone to Diacetone Alcohol . . , . . . . 193
Dehydration of Diacetone Alcohol to Mesityl Oxide . , . . 196 Condensation-Dehydration of Acetone to Mesityl Oxide . . . 196 Hydrogenation of Mesityl Oxide to Methyl Isobutyl Ketone . 198
Review of Processes . . . . . . . . . . . . . . . . . . . . 199 Diacetone Alcohol by Condensation of Acetone . . . . . . . 199 Mesityl Oxide by Dehydration of Diacetone Alcohol , . . . 201 Mesityl Oxide by Condensation-Dehydration of Acetone . . . 207 Methyl Isobutyl Ketone by Hydrogenation of Mesityl Oxide . 208
Process Description . . . . . . . . . , , . . . . . . . . . 211 Process Discussion . . . . . . . . . . . . . . . . . . . 221
Cost Estimates , . . . . . . . . . . . . . . . . . . . . . . 223
Capital Costs , , . . . . . . , . . . . . . . . . . , . . 223 Production Costs . . . . . . . . . . . . . . , . . . . . . 223
12 METHYL ISOBUTYL KETONE BY DIRECT CONDENSATION OF ACETONE . . 233
Chemistry ......................... 233 Review of Processes .................... 235 Process Description .................... 239 Process Discussion ..................... 246 Cost Estimates ....................... 246 Capital Costs ...................... 246 Production Costs ..................... 246
13 METHYL ISOBUTYL KETONE BY OTHER PROCESSES ......... 253
Catalytic Condensation of Isopropanol and Acetone ..... 253 Catalytic Condensation of Isopropanol ........... 253 Oxidation of 4-Methyl-l-pentene .............. 253
APPENDIX A DESIGN AND COST BASIS ................ 255
APPENDIX B PHYSICALPROPERTIES ................. 261
APPENDIX C RAW MATERIAL AND PRODUCT SPECIFICATIONS ....... 265
APPENDIX D SAFETY ....................... 269
APPENDIX E RULE 66 OF THE LOS ANGELES, CALIFORNIA AIR POLLUTION CONTROL DISTRICT .................. 271
CITEDREFERENCES ........................ 273
PATENT REFERENCES BYCOMPANY .................. 313
viii
ILLUSTRATIONS
4.1
4.2
4.3
4.4
5.1
5.2
5.3
5.4
5.5
5.6
7.1
7.2
8.1
8.2
8.3
8.4
8.5
Acetone by Vapor Phase Dehydrogenation of Isopropanol . , 43
Acetone from Propylene by Two-Step Process Effect of Plant Capacity on Capital Investment , , . . , , 53
Acetone from Propylene by Two-Step Process Effect of Propylene Price on Net Production Cost of Acetone . . . . . . . . . . . . . . . . . . . . . . . . . 56
Acetone from Propylene by Two-Step Process Effect of Operating Level and Production Capacity on Net Production Cost of Acetone . . . . . . . . . . . . . 57
Effect of Palladium Ligand and Acid Concentration on Propionaldehyde Formation . . . , . . . . . . . . . . . , 62
Absorption Rate of Various Olefins in 0.1 Molar PdCl, Solution at 20°C . . . . . , . . , . . . . . . . . . . . . 63
Acetone by Direct Oxidation of Propylene . . . . . . . , . 79
Acetone by Direct Oxidation of Propylene Effect of Plant Capacity on Capital Investment . . . . , . 89
Acetone by Direct Oxidation of Propylene Effect of Propylene Price on Net Production Cost of Acetone . . . . . . . . . . . . . . . . . . . . . . . . . 91
Acetone by Direct Oxidation of Propylene Effect of Operating Level and Production Capacity on Net Production Cost of Acetone . . . . , . . , . . . . . 92
Secondary Butanol by Sulfation and Hydrolysis of Normal Butylenes . . . . . . . . . . . . . . . . . . . . . . . . 111
Material Selection Chart for Sulfuric Acid . . . . , . . . 117
Effect of Zinc Content in the Brass Catalyst on the Yield of Methyl Ethyl Ketone . . . . . . . . . . . . . . . . . . 127
Effect of Space Velocity and Temperature on the Yield of Methyl Ethyl Ketone . . . . . . . . . . . . . . . . . . . 128
Effect of Impurities in the Secondary Butanol on the Yield of Methyl Ethyl Ketone . . . . . . . . . . . . . . . 133
Methyl Ethyl Ketone by Dehydrogenation of Secondary Butanol . . . . . . . . . . . . . . . . . . . . . . . . . 141
Methyl Ethyl Ketone from Normal Butylenes by Two-Step Process Effect of Plant Capacity on Capital Investment , . . . . . 150
ix
ILLUSTRATIONS
8.6 Methyl Ethyl Ketone from Normal Butylenes by Two-Step Process Effect of Normal Butylene Price on Net Production Cost of Methyl Ethyl Ketone . . . . . . . , . . . . . . . . . . 152
8.7 Methyl Ethyl Ketone from Normal Butylenes by Two-Step Process Effect of Operating Level and Production Capacity on Net Production Cost of Methyl Ethyl Ketone . . , . . . . . 153
9.1 Absorption of Normal Butylenes in Catalyst Solution , . . 157
9.2 Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes ..,.........., . . . . . . . . . . 173
9.3 Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Effect of Plant Capacity on Capital Investment . . . , , . 184
9.4 Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Effect of Normal Butylene Price on Net Production Cost of Methyl Ethyl Ketone,. . . . . . . . . . , . . . . . . . 186
9.5 Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Effect of Operating Level and Production Capacity on Net Production Cost of Methyl Ethyl Ketone . . . . . . . . 187
11.1 Condensation of Acetone to Diacetone Alcohol Effect of Temperature on the Equilibrium Constant and the Rate Constant . . . . . . . . . . , . . . . . . . . . 195
11.2 Methyl Isobutyl Ketone from Acetone via Mesityl Oxide . . 217
11.3 Methyl Isobutyl Ketone from Acetone via Mesityl Oxide Effect of Plant Capacity on Capital Investment , . . . . . 227
11.4 Methyl Isobutyl Ketone from Acetone via Mesityl Oxide Effect of Acetone Price on Total Production Cost of Methyl Isobutyl Ketone . . . . . . . . . . , . . . . . . . 231
'11.5 Methyl Isobutyl Ketone from Acetone via Mesityl Oxide Effect of Operating Level and Production Capacity on Total Production Cost of Methyl Isobutyl Ketone . . . . , 232
12.1 Methyl Isobutyl Ketone by Direct Condensation of Acetone . 243
ILLUSTRATIONS
12.2 Methyl Isobutyl Ketone by Direct Condensation of Acetone Effect of Plant Capacity on Capital Investment . . . . . . 249
12.3 Methyl Isobutyl Ketone by Direct Condensation of Acetone Effect of Acetone Price on Total Production Cost of Methyl Isobutyl Ketone . . . . . . . . . . . . . . . . . . 251
12.4 Methyl Isobutyl Ketone by Direct Condensation of Acetone Effect of Operating Level and Production Capacity on Total Production Cost of Methyl Isobutyl Ketone , . . . , 252
B.l Mutual Solubility of Methyl Ethyl Ketone and Water as a Function of Temperature . . . . . . . . . . . . . . . . . 264
B.2 Mutual Solubility of Methyl Isobutyl Ketone and Water as a Function of Temperature . . . . . . . . . . . . . . . . 264
Xi
TABLES
2.1
2.2
2.3
2.4
3.1
3.2
3.3
3.4
3.5
4.1
4.2
4.3
4.4
4.5
4.6
4.7
5.1
5.2
5.3
Summary of Economics of Acetone Processes . . . . . , , . 5
Summary of Technical Characteristics of Secondary Butanol and Various Ketone Processes . . . . . . . , . . . 7
Summary of Economics of Secondary Butanol and Methyl Ethyl Ketone Processes . . . . . . . . . . . . . . . . . . 10
Summary of Economics of Methyl Isobutyl Ketone Processes . 12
Acetone Plant Capacities North and South America . . . . . . . . . . . . . . . . . 17
Acetone Plant Capacities Europe.....,......,............. 18
Acetone Plant Capacities Japan and India . . . . . . . . . . . . . . . . . . . . . 19
Methyl Ethyl Ketone Plant Capacities . . , . . . . . . , . 24
Methyl Isobutyl Ketone Plant Capacities . . , . . . , . . 24
Acetone by Dehydrogenation of Isopropanol Patent Summary . . . . . . . . . . . . . . . . . . . . . . 33
Acetone by Vapor Phase Dehydrogenation of Isopropanol Major Process Equipment and Utilities Summary . . . . . . 42
Acetone by Vapor Phase Dehydrogenation of Isopropanol Stream Flows , . . . . . . . . . . . . , . . . . . . . . . 45
Acetone by Vapor Phase Dehydrogenation of Isopropanol Total Capital Investment . . . . . . . . . . . . . , , . . 51
Acetone from Propylene by Two-Step Process Total Capital Investment . . . , . . . , . , , . . . . . . 52
Acetone by Vapor Phase Dehydrogenation of Isopropanol Direct Operating Costs . . . . . . , . . . . . . . . . , . 54
Acetone from Propylene by Two-Step Process Production Costs . . . . . . . . . . . . . . . . . . . , . 55
Acetone by Direct Oxidation of Propylene Patent Summary . . . . . . . . . . . . . . . . . . . . . . 65
Acetone by Direct Oxidation of Propylene Major Process Equipment and Utilities Summary . . , . . . 78
Acetone by Direct Oxidation of Propylene Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 81
xiii
TABLES
5.4
5.5
7.1
7.2
7.3
7.4
8.1
8.2
8.3
8.4
8.5
* 8.6
9.1
Acetone by Direct Oxidation of Propylene Total Capital Investment . . . . . . . . . . . . . . . . . 88
Acetone by Direct Oxidation of Propylene Production Costs . . . . . . . . . , , . . . . . . , . . . 90
Secondary Butanol by Sulfation and Hydrolysis of Normal Butylenes Major Process Equipment and Utilities Summary . . . . . . 109
Secondary Butanol by Sulfation and Hydrolysis of Normal Butylenes Stream Flows . . . . . . . . . . . . . . . . . . . . , . , 113
Secondary Butanol by Sulfation and Hydrolysis of Normal Butylenes Total Capital Investment . . . . . , . . . . . . . . . . . 119
Secondary Butanol by Sulfation and Hydrolysis of Normal Butylenes Production Costs . . . . . . , . . . . . . . . . . . . . . 121
Methyl Ethyl Ketone by Dehydrogenation of Secondary Butanol Patent Summary. . . . . . , . . . . , . . . . . . , . . . 129
Methyl Ethyl Ketone by Dehydrogenation of Secondary Butanol Major Process Equipment and Utilities Summary . . . . . . 139
Methyl Ethyl Ketone by Dehydrogenation of Secondary Butanol Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 143
Methyl Ethyl Ketone by Dehydrogenation of Secondary Butanol Total Capital Investment . . . . . . , . . . . , . , . . . 147
Methyl Ethyl Ketone from Norma1 Butylenes by Two-Step Process Total Capital Investment . , . . . . . . , . , . . . . . . 149
Methyl Ethyl Ketone from Normal Butylenes by Two-Step Process, Production Costs . . . . . . . . . . . . . . . . . . . . . 151
Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Patent Summary . . . . . . . . . . . . . . . . . . . . . . 159
xiv
TABLES
9.2
9.3
9.4
9.5
11.1
11.2
11.3
11.4
11.5
11.6
12.1
12.2
12.3
12.4
12.5
Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Major Process Equipment and Utilities Summary . . . . . .
Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Stream Flows , . . . . . . . . . . . . . . . . . . . . . .
Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Total Capital Investment . . . . . . . . . , . . . . . . .
Methyl Ethyl Ketone by Direct Oxidation of Normal Butylenes Production Costs . . . . . . . . . . . . . . . . . . . . .
Mesityl Oxide by Diacetone Alcohol Dehydration or by Acetone Condensation Patent Summary . . . . . . . . . . . . . . . . . . . . . .
Methyl Isobutyl Ketone by Hydrogenation of Mesityl Oxide Patent Summary . . . . . . . . . . . . . . . . , . . . , ,
Methyl Isobutyl Ketone from Acetone via Mesityl Oxide Major Process Equipment and Utilities Summary . . . . . .
Methyl Isobutyl Ketone from Acetone via Mesityl Oxide Stream Flows . . . . . . . . . . . . . . . . . . . . . . .
Methyl Isobutyl Ketone from Acetone via Mesityl Oxide Total Capital Investment . . . . . . . . . . . . . . . . .
Mesityl Isobutyl Ketone from Acetone via Mesityl Oxide Production Costs . . . , . . . . . . . . . . , . . . . . .
Methyl Isobutyl Ketone by Direct Condensation of Acetone Patent Summary . . . . . . . . . . . . . . . . . . . . . .
Methyl Isobutyl Ketone by Direct Condensation of Acetone Major Process Equipment and Utilities Summary . . . . , ,
Methyl Isobutyl Ketone by Direct Condensation of Acetone Stream Flows . . . . . . . . . . . . . . . . . . . . . . .
Methyl Isobutyl Ketone by Direct Condensation of Acetone Total Capital Investment . . . . . . . . . . . . . . . . .
Methyl Isobutyl Ketone by Direct Condensation of Acetone Production Costs . . . . . . . . . . . . . . . . . . . . .
171
175
183
185
203
209
215
219
225
229
237
242
245
248
250
xv