l Report No. 118 l BUTYROLACTAMandLAUROLACTAM

by ROBERT H. SCHWAAR

and TOHRU YAMADA

September 1977

A private report by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I 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 HYDROCARBONS 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, product, and plant for the United States and Western Europe.

ii CONTENTS

1 INTRODUCTION...... , . . . . 1

2 SUMMARY ...... ...... 3 General Aspects ...... 3 Economic Aspects ...... 3 Technical Aspects ...... 6 Y-Butyrolactam ...... 8 General Aspects ...... 8 Economic Aspects ...... 8 Technical Aspects ...... 11

3 INDUSTRY STATUS ...... 13 Laurolactam ...... 13 Butyrolactam ...... 15

4 FROM VIA . . . . . 19 Chemistry ...... 20 Cyclododecatriene Production ...... 20 Cyclododecatriene ...... 21 Review of Processes ...... 21 Cyclododecatriene Production ...... 21 Removal of Ziegler Catalyst ...... 29 Hydrogenation of Cyclododecatriene ...... 29 Process Description ...... 33 Process Discussion ...... 39 Butadiene Purification ...... 39 Catalyst Removal ...... 40 Removal of Heavy Residue ...... 40 Hydrogenation ...... 40 Processing of Recycle Streams from Other Units ...... 41 Waste Streams ...... 41 Cost Estimates ...... 42 Capital Costs ...... 42 Production Costs ...... 42

5 LAUROLACTAM FROM CYCLODODECANE VIA CYCLODODECANONE . . . . . 51 Chemistry ...... 51 Oxidation of Cyclododecane to Cyclododecanol ...... 52 Dehydrogenation of Cyclododecanol to Cyclododecanone . . . 53 Conversion of Cyclododecanone to Cyclododecanone . . 54

Vii CONTF,NTS

5 LAUROLACTAM FROM CYCLODODECANE VIA CYCLODODECANONE (Continued)

Hydroxylamine Preparation ...... 54 Rearrangement of Cyclododecanone Oxime to Laurolactam . . 55 Review of Processes ...... 56 Oxidation of Cyclododecane to Cyclododecanol ...... 56 Dehydrogenation of Cyclododecanol to Cyclododecanone . . . 63 Conversion of Cyclododecanone to Cyclododecanone Oxime . . 67 Production of ...... 72 Rearrangement of Cyclododecanone Oxime to Laurolactam . . 74 Ammonium Sulfate Recovery ...... 83 Purification of Laurolactam ...... 83 Coproduction of Laurolactam and ...... 84 Process Description ...... 90 Oxidation of Cyclododecane to Cyclododecanol ...... 92 Dehydrogenation of Cyclododecanol to Cyclododecanone . . . 92 Conversion of Cyclododecanone to Cyclododecanone Oxime . . 93 Rearrangement of Cyclododecanone Oxime to Laurolactam . . 93 Purification of Laurolactam ...... 94 Ammonium Sulfate Recovery ...... 95 Process Discussion ...... 102 Recovery of ...... 102 Recovery of Unreacted Cyclododecane ...... 102 Oximation ...... 103 Hydroxylamine Sulfate ...... 103 Ammonium Sulfate By-Product Handling ...... 104 Product Handling ...... 105 Tempered Water System ...... 105 Cost Estimates ...... 105 Capital Costs ...... 105 Production Costs ...... 106

6 LAUROLACTAM FROM CYCLODODECANE VIA PHOTOOXIMATION ... . . 117 Chemistry ...... 117 Review of Processes ...... 117 Cyclododecanone Oxime by Photooximation ...... 117 Rearrangement of Cyclododecanone Oxime Hydrochloride to Laurolactam ...... 124 Purification of Laurolactam ...... 125 Process Description ...... 129 Preparation ...... 129 Photooximation ...... 131 Rearrangement ...... 131

viii CONTENTS

6 LAUROLACTAM FROM CYCLODODECANE VIA PHOTOOXIMATION (Continued)

Purification ...... 132 Ammonium Sulfate Recovery ...... 133 Chlorinated Waste Disposal ...... 133 Process Discussion ...... 141 Photooximation Productivity ...... 141 Photooximation Reaction Selectivity ...... 141 Operation Without a Solvent ...... 142 Form of the Oxime Hydrochloride ...... 143 Rearrangement Reaction ...... 143 Purification of Laurolactam ...... 143 Product Handling ...... 144 Ammonium Sulfate By-Product Handling ...... 144 Tempered Water System ...... 144 Materials of Construction ...... 145 Cost Estimates ...... 145 Capital Costs ...... 145 Production Costs ...... 145

7 OTHER LAUROLACTAM PROCESSES ...... 157 Cyclododecanone Oxime from Cyclododecane via Nitrocyclododecane ...... 157 Cyclododecanone Oxime from Cyclododecatriene via Chlorocyclododecadiene Oxime ...... 159 Cyclododecanol or Cyclododecanone from Cyclododecatriene via Epoxycyclododecadiene ...... 159 Cyclododecene from Cyclododecatriene ...... 160 Cyclododecanol from Cyclododecene ...... 160 Cyclododecanone Oxime from Cyclododecene ...... 160 Laurolactam from Cyclododecene via 0x0 Reaction to Cyclododecane Carboxylic Acid ...... 161 12-Aminododecanoic Acid from Cyclododecene via Nitrocyclododecanone ...... 166 12-Aminododecanoic Acid from Cyclohexanone via l,l'-Peroxydicyclohexylamine ...... 166 Miscellaneous Processes ...... 167

8 BUTYROLACTAM VIA BUTYROLACTONE ...... 169 Chemistry ...... 170 Butyrolactone from Maleic Anhydride ...... 170 Butyrolactone from 1,4-Butanediol ...... 171 Conversion of Butyrolactone to Butyrolactam ...... 172

ix CONTENTS

8 BUTYROLACTAM VIA BUTYROLACTONE (Continued)

Review of Processes ...... 172 Butyrolactone from Maleic Anhydride by Liquid-Phase Processes ...... 172 Butyrolactone from Maleic Anhydride by Vapor-Phase Processes ...... 187 Butyrolactone from 1,4-Butanediol ...... 187 Butyrolactone from Other Starting Materials ...... 188 Ethylene ...... 188 Tetrahydrofuran ...... 188 0x0 Process ...... 189 Conversion of Butyrolactone to Butyrolactam ...... 190 Butyrolactone from Maleic Anhydride ...... 191 Process Description ...... 191 Process Discussion ...... 197 Choice of Process ...... 197 Feed Preparation ...... 197 Reactor Design ...... 198 Solvent ...... 198 Product Purification ...... 198 Waste Products ...... 199 Materials of Construction ...... 199 Cost Estimates ...... 200 Capital Costs ...... 200 Production Costs ...... 200 Butyrolactone from 1,4-Butanediol ...... 208 Process Description ...... 208 Process Discussion ...... 214 Materials of Construction ...... 214 Waste Products ...... 214 Cost Estimates ...... 215 Capital Costs ...... 215 Production Costs ...... 216 Conversion of Butyrolactone to Butyrolactam ...... 223 Process Description ...... 223 Process Discussion ...... 229 Reaction Conditions ...... 229 Selection of Reactor Configuration ...... 229 Ammonia Recovery ...... 229 Final Distillation of Butyrolactam Product ...... 230 Ammonia Supply...... 230 Heating Media ...... 230 Materials of Construction ...... 230 Waste Disposal ...... 231

X CONTENTS

8 BUTYROLACTAM VIA BUTYROLACTONE (Continued)

Cost Estimates ...... 231 Capital Costs ...... 231 Production Costs ...... 232

9 OTHER BUTYROLACTAM PROCESSES ...... 239 Review of Processes ...... 239 Butyrolactam from Maleic Anhydride ...... 239 Butyrolactam from Succinonitrile ...... 246 Butyrolactam from Other Starting Materials ...... 247 Butyrolactam from Maleic Anhydride ...... 248 Process Description ...... 248 Process Discussion ...... 256 Feed Preparation ...... 256 First-Stage Reactor ...... 256 Second-Stage Reactor ...... 256 Recycle Water Stripping ...... 257 Product Purification ...... 257 Waste Products ...... 257 Materials of Construction ...... 258 Cost Estimates ...... 258 Capital Costs ...... 258 Production Costs ...... 259

APPENDIX A DESIGN AND COST BASES ...... 267

APPENDIX B PROPERTIES OF RAW MATERIALS AND INTERMEDIATES . . . 269

CITED REFERENCES...... 279

PATENT REFERENCES BY COMPANY ...... 299

Xi ILLUSTRATIONS

4.1 Cyclododecane from Butadiene via Cyclododecatriene Process Flow Diagram ...... 307 4.2 Cyclododecane from Butadiene via Cyclododecatriene Effect of Plant Capacity on Total Fixed Capital . . . . . 47

4.3 Cyclododecane from Butadiene via Cyclododecatriene Effect of Operating Level and Plant Capacity l on Production Cost ...... 50 5.1 Laurolactam from Cyclododecane via Cyclododecanone . Process Flow Diagram ...... 309 5.2 Laurolactam from Cyclododecane via Cyclododecanone Effect of Plant Capacity on Total Fixed Capital . . . . . 111 5.3 Laurolactam from Cyclododecane via Cyclododecanone Effect of Cyclododecane Price on Production Cost . . . . 114 5.4 Laurolactam from Cyclododecane via Cyclododecanone Effect of Operating Level and Plant Capacity on Production Cost ...... 115 6.1 Laurolactam from Cyclododecane by Photooximation Process Flow Diagram ...... , . . 315 6.2 Laurolactam from Cyclododecane by Photooximation Effect of Plant Capacity on Total Fixed Capital . . . . . 151 6.3 Laurolactam from Cyclododecane by Photooximation Effect of Cyclododecane Price on Production Cost . . . . 154 6.4 Laurolactam from Cyclododecane by Photooximation Effect of Operating Level and Plant Capacity on Production Cost ...... 155 7.1 Routes from Cyclododecatriene to Laurolactam ...... 158 8.1 Y-Butyrolactone from Maleic Anhydride Process Flow Diagram ...... 321 8.2 y-Butyrolactone from Maleic Anhydride Effect of Plant Capacity on Total Fixed Capital . . . . . 204 8.3 y-Butyrolactone from Maleic Anhydride Effect of Operating Level and Plant Capacity on Production Cost ...... 205 8.4 Y-Butryolactone from 1,4-Butanediol Process Flow Diagram ...... 323

xiii ILLUSTRATIONS

8.5 Y-Butyrolactone from 1,4-Butanediol Effect of Plant Capacity on Total Fixed Capital . . . . . 219 8.6 Y-Butyrolactone from 1,4-Butanediol Effect of Operating Level and Plant Capacity on Production Cost ...... 222 8.7 Conversion of Y-Butyrolactone to Y-Butyrolactam Process Flow Diagram ...... 325 8.8 Conversion of Y-Butyrolactone to Y-Butyrolactam Effect of Plant Capacity on Total Fixed Capital . . . . . 235 8.9 Conversion of Y-Butyrolactone to Y-Butyrolactam Effect of Operating Level and Plant Capacity on Production Cost ...... 238 9.1 Y-Butyrolactam from Maleic Anhydride Process Flow Diagram ...... 327 9.2 Y-Butyrolactam from Maleic Anhydride Effect of Plant Capacity on Total Fixed Capital . . . . . 263 9.3 Y-Butyrolactam from Maleic Anhydride Effect of Operating Level and Plant Capacity on Production Cost ...... 266 B.l Vapor Pressures of Butyrolactam and Related Compounds.. . 276 B.2 Vapor Pressures of Cyclododecane and Related Compounds...... 277 B.3 Vapor Pressures of Laurolactam and Related Compounds . . 278

xiv TABLES

2.1 ,Summary of Cost Estimates for Laurolactam Manufacture . . 4 2.2 Summary of Cost Estimates for Y-Butyrolactone and Y-Butyrolactam Manufacture ...... 9

3.1 1,4-Butanediol, Tetrahydrofuran, Butyrolactone, and Butyrolactam Production Plants ...... 17 4.1 Cyclododecatriene from Butadiene Through the Use of a Ziegler Catalyst Summary of Patents on Catalyst Systems ...... 24 4.2 Cyclododecatriene from Butadiene Through the Use of a Ziegler Catalyst Summary of Other Patents ...... 28 4.3 Hydrogenation of Cyclododecatriene to Cyclododecane Patent Summary ...... 30 4.4 Cyclododecane from Butadiene via Cyclododecatriene Bases and Assumptions ...... 34 4.5 Cyclododecane from Butadiene via Cyclododecatriene Major Equipment and Utilities Summary ...... 36 4.6 Cyclododecane from Butadiene via Cyclododecatriene Stream Flows ...... 38 4.7 Cyclododecane from Butadiene via Cyclododecatriene Total Capital Investment ...... 44 4.8 Cyclododecane from Butadiene via Cyclododecatriene Major Capital Equipment Costs ...... 46 4.9 Cyclododecane from Butadiene via Cyclododecatriene Production Costs ...... 48 5.1 Oxidation of Cyclododecane to Cyclododecanol Patent Summary ...... 57 5.2 Dehydrogenation of Cyclododecanol to Cyclododecanone Patent Summary ...... 64 5.3 Oximation of Cyclododecanone Patent Summary ...... 68 5.4 Rearrangement of Cyclododecanone Oxime to Laurolactam Patent Summary ...... 75 5.5 Rearrangement of Cycloalkanone to Lactams Patent Summary ...... 81

xv TABLES

5.6 Purification of Laurolactam PatentSummary ...... 86 - 5.7 Purification Processes Possibly Applicable to Laurolactam Patent Summary ...... 88 5.8 Laurolactam from Cyclododecane via Cyclododecanone Bases and Assumptions ...... 91 a- 5.9 Laurolactam from Cyclododecane via Cyclododecanone Major Equipment and Utilities Summary ...... 96 5.10 Laurolactam from Cyclododecane via Cyclododecanone Stream Flows ...... 99 5.11 Laurolactam from Cyclododecane via Cyclododecanone Total Capital Investment ...... 108 5.12 Laurolactam from Cyclododecane via Cyclododecanone Major Capital Equipment Costs ...... 110 5.13 Laurolactam from Cyclododecane via Cyclododecanone Production Costs ...... 112 a- 6.1 Laurolactam from Cyclododecane by Photooximation Patent Summary ...... 119 6.2 Rearrangement of Cyclododecanone Oxime Produced by Photooximation Patent Summary ...... 126 6.3 Purification of Laurolactam Produced by Photooximation Patent Summary ...... 128 6.4 Laurolactam from Cyclododecane via Photooximation Bases and Assumptions ...... 130 6.5 Laurolactam from Cyclododecane via Photooximation Major Equipment and Utilities Summary ...... 134 a- 6.6 Laurolactam from Cyclododecane by Photooximation Stream Flows ...... 137 6.7 Laurolactam from Cyclododecane by Photooximation Waste Treatment ...... 140 6.8 Laurolactam from Cyclododecane by Photooximation a Total Capital Investment ...... 148 6.9 Laurolactam from Cyclododecane by Photooximation Major Capital Equipment Costs ...... 150

xvi TABLES

6.10 Laurolactam from Cyclododecane by Photooximation Production Costs ...... 152 6.11 Laurolactam from Cyclododecane by Photooximation Sensitivity of Production Cost to Selectivity ...... 156

7.1 Selective Hydrogenation of Cyclododecatriene to Cyclododecene Patent Summary ...... 162 8.1 Y-Butyrolactone from Maleic Anhydride by Liquid-Phase Processes Patent Summary ...... 174

8.2 Y-Butyrolactone from Maleic Anhydride by Vapor-Phase Process Patent Summary ...... 178 8.3 Y-Butyrolactone from Other Starting Materials Patent Summary ...... 180 8.4 Conversion of Y-Butyrolactone to Y-Butyrolactam Patent Summary ...... 183 a 8.5 Y-Butyrolactone from Maleic Anhydride Bases and Assumptions ...... 192 8.6 Y-Butyrolactone from Maleic Anhydride Major Equipment and Utilities Summary ...... 194 8.7 Y-Butyrolactone from Maleic Anhydride Stream Flows ...... 196 8.8 Y-Butyrolactone from Maleic Anhydride Total Capital Investment ...... 202 8.9 Y-Butyrolactone from Maleic Anhydride Major Capital Equipment Costs ...... 203 8.10 Y-Butyrolactone from Maleic Anhydride Production Costs ...... 206 8.11 Y-Butyrolactone from 1,4-Butanediol Bases and Assumptions ...... 209 8.12 Y-Butyrolactone from 1,4-Butanediol - Major Equipment and Utilities Summary ...... 211 8.13 Y-Butyrolactone from 1,4-Butanediol Stream Flows ...... 213 8.14 Y-Butyrolactone from 1,4-Butanediol Total Capital Investment ...... 217 a xvii TABLES

8.15 Y-Butyrolactone from 1,4-Butanediol Major Capital Equipment Costs ...... 218 8.16 Y-Butyrolactone from 1,4-Butanediol Production Costs ...... 220

8.17 Conversion of Y-Butyrolactone to Y-Butyrolactam Bases and Assumptions ...... 224

8.18 Conversion of Y-Butyrolactone to Y-Butyrolactam Major Equipment and Utilities Summary ...... 226 8.19 Conversion of Y-Butyrolactone to Y-Butyrolactam Stream Flows ...... 228 8.20 Conversion of Y-Butyrolactone to Y-Butyrolactam Total Capital Investment ...... 233

8.21 Conversion of Y-Butyrolactone to Y-Butyrolactam Major Capital Equipment Costs ...... 234

8.22 Conversion of Y-Butyrolactone to Y-Butyrolactam Production Costs ...... 236

9.1 Y-Butyrolactam from Starting Materials Other Than Y-Butyrolactone a- Patent Summary ...... 240

9.2 Y-Butyrolactam from Maleic Anhydride Bases and Assumptions ...... ; .... 249 9.3 Y-Butyrolactam from Maleic Anhydride Major Equipment and Utilities Summary ...... 252

9.4 Y-Butyrolactam from Maleic Anhydride Stream Flows ...... 254

9.5 Y-Butyrolactam from Maleic Anhydride Total Capital Investment ...... 261

9.6 Y-Butyrolactam from Maleic Anhydride Major Capital Equipment Costs ...... 262 a 9.7 Y-Butyrolactam from Maleic Anhydride Production Costs ...... 264 B.l Butadiene Specifications (Commercial Grade) ...... 271 B.2 Properties of Selected Compounds ...... 272 B.3 Properties of Maleic Anhydride, Butyrolactone, and Butyrolactam ...... 274 B.4 1,4-Butanediol Properties ...... 275

xviii