Report No. 31

HEXAMETHYLENE DIAMINE

by PARK L. MORSE

with contributions by Clifford A. Hampel, Consultant

November 1967

A private report by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA CONTENTS

1 INTRODUCTION...... 1

2 SUMMARY ...... 3

3 INDUSTRY STATUS ...... 13

4 CHEMISTRY ...... 17 Adipic Acid Route to Adiponitrile ...... 17 Adiponitrile from Electrolytic Hydrodimerization of Acrylonitrile ...... 17 Adiponitrile from 1,3-Butadiene ...... 18 HMDA from Adiponitrile ...... 19 HMDA from a Diol Intermediate ...... 19

5 ADIPONITRILE FROM ADIPIC ACID ...... 21 Review of Process Information ...... 21 Raw Materials and Ratio of Reactants ...... 21 Catalysts ...... 21 By-Products ...... 21 Reaction Temperature and Pressure ...... 25 Yield and Rate of Reaction ...... 25 Reactor Design ...... 26 Purification of Adiponitrile ...... 27 Description of Design Case ...... 31 Discussion of Design Case ...... 43

6 ADIPONITRILE FROM ACRYLONITRILE ...... 45 Review of Process Information ...... 45 Electrolytic Hydrodimerization ...... 48 Basic Information ...... 48 By-Products ...... 49 Yield, Conversion, and Selectivity ...... 50 CellDesign ...... 50 Purification of Adiponitrile ...... 50 Description of Design Case ...... 51 Discussion of Design Case ...... 54

iii CONTENTS

7 ADIPONITRILE FROM BUTADIENE ...... 63 Review of Process Information ...... 63 Dichlorobutene from Butadiene ...... 63 1,4-Dicyanobutene from Dichlorobutene ...... 72 Isomerization of 1,4-Dicyanobutene-2 ...... 74 Adiponitrile from Dicyanobutene ...... 75 Purification of Intermediates and Products ...... 76 Description of Design Case ...... 76 Dichlorobutene from Butadiene ...... 76 Dicyanobutene from Dichlorobutene ...... 78 Adiponitrile from Dicyanobutene ...... 81 Purification of Adiponitrile ...... 95 Discussion of Design Case ...... 101

8 HEXAMETHYLENEDIAMINE FROMADIPONITRILE...... 111 Review of Process Information ...... 111 Description of Design Case ...... 117 Discussion of Design Case ...... 127

9 HEXAMETHYLENEDIAMINE FROM DIOL INTERMEDIATE ...... 129 Review of Process Information ...... 129 Description of Design Case ...... 136 Cyclohexane Oxidation ...... 137 Esterification ...... 138 Hydrogenation ...... 139 1,6-Hexanediol Purification ...... 142 Ammonolysis ...... 142 Purification of HMDA ...... 144 Discussion of Design Case ...... 169

10 HEXAMETHYLENEDIAMINE FROM ETHYLENE...... 173 Incentive to Manufacture 1,4-Dichlorobutane from Ethylene . 173 Effect of Pressure and Temperature ...... 173 Use of Solvent ...... 175 Economic Considerations ...... 175

iv CONTENTS

11 CAPITAL AND PRODUCTION COSTS ...... 177 BMDA from Adipic Acid ...... 177 HMDA from Acrylonitrile ...... 184 BMDA from Butadiene ...... 190 HMDA from Diol Intermediate ...... 196

APPENDIX A DESIGN AND COST BASIS,DEFINITIONS ...... 203

APPENDIX B PHYSICAL PROPERTIES ...... 207

APPENDIXC RAW MATERIAL SPECIFICATION AND PRODUCT CHARACTERISTICS ...... 209

APPENDIX D HANDLING AND SAFETY ...... 213

REFERENCES ...... 215

SUPPLEMENTAL REFERENCES...... 227 ILLUSTRATIONS

5.1 Crude Adiponitrile from Adipic Acid ...... 35

5.2 Purification of Adiponitrile ...... 39

6.1 Adiponitrile from Acrylonitrile ...... 57

7.1 Chemical Routes from Butadiene to HMDA ...... 65

7.2 Adiponitrile from Butadiene: Dichlorobutene Manufacture ...... 85

7.3 Adiponitrile from Butadiene: Dicyanobutene Manufacture ...... 87

7.4 Adiponitrile from Butadiene: Crude Adiponitrile Manufacture ...... 89

7.5 Purification of Adiponitrile ...... 97

8.1 HMDA by Hydrogenation of Adiponitrile ...... 121

8.2 Purification of HMDA Made from Adiponitrile ...... 123

9.1 HMDA from a Diol Intermediate ...... 133

9.2 HMDA from a Diol Intermediate Cyclohexane Oxidation ...... 149

9.3 HMDA from a Diol Intermediate Esterification ...... 151

9.4 HMDA from a Diol Intermediate Hydrogenation ...... 153

9.5 HMDA from a Diol Intermediate Purification of 1,6-Hexanediol ...... 155

9.6 HMDA from a Diol Intermediate Ammonolysis ...... 157

9.7 HMDA from a Diol Intermediate Purification of HMDA ...... 159

vii -.

ILLUSTRATIONS

11.1 HMDA from Adipic Acid Effect of Operating Level and Plant Capacity on Production Cost ...... 183

11.2 HMDA from Acrylonitrile Effect of Operating Level and Plant Capacity on Production Cost ...... 189

11.3 HMDA from Ehtadiene Effect of Operating Level and Plant Capacity on Production Cost ...... 195

11.4 HMDA from a Diol Intermediate Effect of Operating Level and Plant Capacity on Production Cost ...... 201

viii TABLES

2.1 Comparison of Process Costs for Producing I-MDA ...... 6

2.2 Technical Comparison of Processes for Production of BMDA . 11

3.1 Plant Capacity in the United States ...... 15

5.1 Adiponitrile from Adipic Acid Summary of Processes ...... 23

5.2 Purification of Adiponitrile Summary of Processes ...... 29

5.3 Adiponitrile from Adipic Acid Production and Purification of Adiponitrile Major Process Equipment and Utilities Summary ...... 34

5.4 Adiponitrile from Adipic Acid Production of Adiponitrile StreamFlows...... 37

5.5 Adiponitrile from Adipic Acid Purification of Adiponitrile Stream Flows ...... 41

6.1 Adiponitrile from Acrylonitrile Summary of Processes ...... 47

6.2 Adiponitrile from Acrylonitrile Major Process Equipment and Utilities Summary ...... 57

6.3 Adiponitrile from Acrylonitrile Stream Flows ...... 61

7.1 Adiponitrile from Butadiene Summary of Processes ...... 67

7.2 Adiponitrile from Butadiene Purification of Dicyanobutene Summary of Processes ...... 71

ix TABLES

7.3 Adiponitrile from Butadiene Major Process Equipment and Utilities Summary ...... 84

7.4 Adiponitrile from Butadiene StreamFlows...... 91

7.5 Purification of Adiponitrile Major Process Equipment List ...... 97

7.6 Purification of Adiponitrile Derived from Butadiene StreamFlows...... 99

8.1 I-MDA from Adiponitrile Summary of Processes...... 113

8.2 Purification of BMDA Summary of Processes ...... 116

8.3 BbIDA from Adiponitrile Major Process Equipment and Utilities Summary ...... 120

8.4 BMDA from Adiponitrile StreamFlows...... 125

9.1 BMDA from Diol Intermediate Summary of Processes ...... 131

9.2 BMDA from Diol Intermediate Major Process Equipment and Utilities Summary ...... 146

9.3 BMDA from Diol Intermediate StreamFlows...... 161

11.1 BMDA from Adipic Acid Process Unit and Utilities Investment ...... 178

11.2 BMDA from Adipic Acid Total Capital Investment ...... 179

11.3 BMDA from Adipic Acid Production Costs ...... 181

X TABLES

11.4 HMDA from Acrylonitrile Process Unit and Utilities Investment ...... 185

11.5 HMDA from Acrylonitrile Total Capital Investment ...... 186

11.6 HMDA from Acrylonitrile Production Costs ...... 187

11.7 I-MDA from Butadiene Process Unit and Utilities Investment ...... 191

11.8 HMDA from Butadiene Total Capital Investment ...... 192

11.9 HMDA from Butadiene Production Costs ...... 193

11.10 HMDA from Diol Intermediate Process Unit and Utilities Investment ...... 197

11.11 HMDA from Diol Intermediate Total Capital Investment ...... 198

11.12 HMDA from Diol Intermediate Production Costs ...... 199

xi