PROCESS ECONOMICS PROGRAM

SRI INTERNATIONAL Abstract Menlo Park, California 94025 Process Economics Program Report No. 54B

NYLON 66

(September 1987)

This updated report on nylon 66 deals also with its intermediates adipic acid and hexamethylenedlamine.

Commercially, adipic acid can be made either from cyclohexane or phenol. Several versions of the cyclohexane process, with variations on catalyst, reactor type, and recovery of waste streams, are evalu- ated. Their economies are generally comparable. The phenol process under most circumstances is less economical than the cyclohexane process. A process under development starting from butadiene is also evaluated. Other processes for making adiplc acid, including one from waste nylon 66 which is used commercially in a small way, and several others of academic interest only, are briefly described and discussed.

Hexamethylenediamineis made commercially from adlpic acid, butadiene, or acrylonitrile. The process from adiplc acid is an old one, still surviving because of depreciated equipment and captive adipic acid. The butadiene process can use either the chlorination route or the hydrocyanation route, with the latter being more eco- nomical. The process starting from acrylonitrile involves electro- hydrodimerization. There are three versions: using an undivided cell, using a divided cell and an emulsion, and using a divided cell and a solution. The first-named version is more economical than the other two. All these processes are evaluated in detail In this report. In addition, a process starting from caprolactam, used commercially on a small scale, a process via 1,6-hexanediol once used by Celanese, and several other processes are briefly evaluated or discussed.

Nylon 66 is usually produced via the formation of a nylon salt. The manufacture of nylon salt as a 63% solution or in solid form is evaluated. Nylon resins of various forms, standard grade, pigmented grades, compounded grades, and extrusion grade, are evaluated. Both the continuous process and the batch process are considered and discussed.

Economics of nylon 66 fibers (carpet staple, carpet yarn, tire cord, textile yarn, hosiery monofilament) are updated from data in previous reports.

PEP 85 Y. C. Yen S-Y wu Report No. 5 4 B -

0 NYLON 6 6

SUPPLEMENT 6

YEN-CHEN YEN and SHIH-YUEH WU

with contributions by YON-LIEN WU, WEN-FA LIN, CHIH-WEI LEE and REN-BEN CHEN

September 1987

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 HANDBOOKProgram covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers I I 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 compsny, prod- uct, and plant for the United States and Western Europe.

ii Revised Jan. 1988

CONTENTS

1 INTRODUCTION...... 1

2 SUMMARY ...... 3 Economic Aspects...... 3 Technical Aspects ...... 9 Adipic Acid from Cyclohexane--The Base Case ...... 9 Adipic Acid from Cyclohexane--RA by the Hydroperoxide Process ...... 9 Adipic Acid from Cyclohexane--RA by the Boric Acid Process ...... 11 Adipic Acid from Cyclohexane--NitricAcid Oxidation of RAwithReactorCooling ...... 11 Adipic Acid from Phenol ...... 11 Adlpic Acid from Butadiene ...... 11 HMDA from Adiplc Acid ...... 12 BMDA from Butadlene via Chlorination ...... 12 HMDA from Butadlene via Hydrocyanation ...... 13 HMDA from Acrylonitrile via Electrohydrodimerization in Solution ...... 14 HMDA from Acrylonitrile via Electrohydrodimerization in Emulsion ...... 15 HMDA from Acrylonitrile via Electrohydrodimerization in an Undivided Cell ...... 15 Nylon Salt Solution from Adlpic Acid and HMDA ...... 16 Solid Nylon Salt ...... 16 Nylon 66 Resin ...... 16 Carpet Staple ...... 17 Carpet Yarn ...... 17 TireCord ...... 17 Textile Yarn...... 18 Hosiery Monofilament ...... 18

3 INDUSTRY STATUS ...... 19 Nylon66 ...... 19 Hexamethylenediamine ...... 27 AdipicAcid ...... 27

4 ADIPIC ACID FROM CYCLOHEXARE ...... 33 Chemistry ...... zi Cyclohexane to KA ...... RAtoAdipicAcid ...... 36

Iii CONTENTS

4 ADIPIC ACID FROM CYCLOHEXANE (Continued) Review of Processes ...... Cyclohexane to KA--Processes ...... Cyclohexane to RA--Reactors ...... 40 Cyclohexane to RA--Product Recovery ...... 41 Cyclohexane to KA--Aqueous Waste Stream Treatment .... 42 RA to Adipic Acid--The Reaction System ...... 43 KA to Adipic Acid--Adipic Acid Recovery ...... 44 ICAto Adipic Acid--Purge Stream Treatment ...... 44 Adipic Adic by One-Step Air Oxidation of Cyclohexane ... 45 Other Processes for Making Adiplc Acid from Cyclohexane ...... Process Description ...... E- Process Discussion ...... 63 Cost Estimates...... 66 Cyclohexane Oxidation by the Hydroperoxide Process .... 66 Cyclohexane Oxidation by the Boric Acid Process ..... 67 Utilization of Aqueous Waste Stream ...... 68 Oxidation of RA to Adipic Acid Without Large Recycle ... 69 Summary ...... 70 Adipic Acid as a By-product of Caprolactam Production ... 72

5 ADIPIC ACID FROM PHENOL VIA CYCLOHEXANOL ...... 93 Process Description ...... 93 Process Discussion ...... 100 Cost Estimates...... 100 Adipic Acid from Phenol via Cyclohexanol ...... 102

6 ADIPICACID FROM BUTADIENE ...... 111 Chemistry ...... 111 Review of Processes ...... 116 Mipic Acid by Carbonylation of Butadiene ...... 116 Catalyst Preparation and Recovery ...... 116 First Hydroesterification ...... 116 Second Hydroesterification ...... 117 Hydrolysis ...... 117 Purification ...... 117 An Alternative Second Step ...... 118 Other Processes ...... 118

iV CONTENTS

6 ADIPIC ACID FROM BUTADIENE (Continued) Process Description ...... 119 Process Discussion ...... 136 Cost Estimates ...... 137

7 OTHER PROCESSES FOR MAKING ADIPIC ACID ...... 145 Mipic Acid from Waste Nylon 66 ...... 145 Mipic Acid by Biochemical Processes ...... 145 Mipic Acid from Cyclohexene ...... 146 Mipic Acid by Carbonylation of Diol, Ether, or Lactone . . 146 Mlpic Acid by Oxidation of Chlorocyclohexane ...... 146 Mipic Acid from Cyclohexylphenyl Ketone ...... 147 Other Processes ...... 147

8 HEXAMETHYLENEDIAMINE FROM ADIPIC ACID ...... 149 Chemistry ...... 149 Review of Processes ...... 151 Conversion of Mipic Acid to Adiponitrile ...... 152 Purification of Adiponitrile ...... 152 Hydrogenation of Adiponitrile to HMDA ...... 152 Purification of HMDA ...... 153 Direct Production of HMDA from Mipic Acid ...... 154 Process Description ...... 154 Process Discussion ...... 169 Cost Estimates ...... 170

9 HEXAKETHYLENE DIAMINE FROM BUTADIENE VIA DICHLOROBUTENE AND DICYANOBUTENE ...... 177 Chemistry ...... 177 Butadiene to Dlchlorobutene ...... 177 Dlchlorobutene to Dicyanobutene ...... 178 Dicyanobutene to Adiponitrile ...... 178 Review of Processes ...... 178 Process Description ...... 179 Process Discussion ...... 195 Cost Estimates ...... 195

10 HEXAMETHYLENEDIAMINEFROM BUTADIENE VIA HYDROCYANATION TO ADIPONITRILE ...... 201 Chemistry ...... 201 Review of Processes ...... 202

V CONTENTS

10 RBXAMETRYLENEDIAMINE FROM BUTADIENE VIA HYDROCYANATION TO ADIPONITRILE (Continued) Process Description ...... 203 Process Discussion . . . - ...... '...... 208 Cost Estimates . . . . . , ...... 208

11 RRXAMRTEIYLENEDIAMINEPROM ACRYLONITRILE VIA ADIPONITRILE BY ELECTRORYDRODIMERIZATION ...... 223 Chemistry ...... 223 Review of Processes ...... 225 Membrane Cell with Acrylonitrile in Solution ...... 225 Membrane Cell with Acrylonitrile in Aqueous Emulsion ... 226 Undivided Cell ...... 226 A process for Making RMDA from Acrylonitrile via Adiponitrile by Electrohydrodimerizationin Solution ... 228 Process Description ...... 228 Process Discussion ...... 242 Cost Estimates...... 242 A Process for Making RMDA via Adiponitrile by Electrohydrodimerizationof Acrylonitrile in Emulsion ... 247 Process Description ...... 247 Process Discussion ...... 257 Cost Estimate ...... 257 A Process for Making BMDA from Acrylonitrile via Adiponitrile by Electrohydrodimerizationin an Undivided Cell ...... 262 Process Description ...... 262 Process Discussion ...... 272 Cost Estimates ...... 272 Comparison of the Processes ...... 273 12 OTRER PROCESSES FOR PREPARATION OF REXAMRTRYLENEDIAMINE . . 279 0- Processes for Making Adiponitrile ...... 279 Amalgam Process Starting with Acrylonitrile ...... 279 Catalytic Dimerization of Acrylonitrile ...... 280 Other Processes for Producing Adiponitrile ...... ' 280 Processes for Making UMDA from Other Raw Materials ..... 280 HMDA from Caprolactam ...... 280 0 BHDA from Cyclohexane via 1,6-Rexanediol (the Diol Process) ...... 283 RMDA from Propylene and Ally1 Chloride ...... 285 Other Processes for Producing BMDA ...... 287 CONTENTS

13 NTLONSALT ...... 289 Chemistry ...... 289 Review of Processes ...... 289 A Process for Producing Nylon Salt Solution ...... 290 Process Description ...... 290 Process Discussion ...... 296 Cost Estimates...... 296 A Process for Producing Solid Nylon Salt ...... 300 Process Description ...... 300 Process Discussion ...... 305 Cost Estimates ...... 305

14 NTLONRESINS ...... 309 Chemistry ...... 309 Review of Processes ...... 309 Process Description ...... 311 Process Discussion ...... 321 Cost Estimates ...... 324 Batch Process for Producing Nylon 66 Resin ...... 333 Nylon Resin from Waste Fiber ...... 334

15 NYLON 66 FIBER...... 343

APPENDIX A PRYSICALDATA ...... 367

PATENT SUMMARYTABLES...... 379

CITEDREFERENCES ...... 481

PATENT REFERENCES...... 517 l

0

vii TABLES

2.1 Adipic Acid (Polymer Grade) Economics ...... 4 2.2 HexamethylenediamineEconomics ...... 6 2.3 Nylon Salt Economics ...... 7 2.4 Nylon Resins (Standard Grade) Economics ...... 8 l 2.5 Nylon Fiber Economics ...... 10 3.1 Nylon 66 Producers in the United States (1986) ...... 20 3.2 Nylon 66 Producers in Western Europe (1986) ...... 21 3.3 Nylon 66 Producers in Countries Outside of United States and Western Europe (1986) ...... 22 3.4 Consumption of Nylon 66 (1983) ...... 23 3.5 U.S. Nylon Fiber Demand by Market Segment (1983) ...... 25 3.6 U.S. Nylon 66 Fiber Demand by Market Segment ...... 26 3.7 U.S. Consumption of Nylon 66 Resins by End-Use (1984) ...... 26 3.8 World Hexamethylenediamine Producers (1986) . . , ...... 29 3.9 Applications of Adipic Acid ...... 30 3.10 World Adipic Acid Producers (1986) ...... 31

4.1 Cyclohexanol/Cyclohexanonefrom Cyclohexane by Catalytic Oxidation Patent Summary ...... 381 4.2 Cyclohexanol/Cyclohexanonefrom Cyclohexane by Hydroperoxide Process Patent Summary ...... 384 4.3 Cyclohexanol/Cyclohexanonefrom Cyclohexane by Boric Acid Process Patent Summary ...... 387

iX TABLES

4.4 Treatment of Reaction Product from Cyclohexane Oxidation Patent Summary ...... 389 4.5 Treatment of the Aqueous Waste Stream from Oxidation of Cyclohexane Patent Summary ...... 391 4.6 Adipic Acid from Cyclohexanol/Cyclohexanoneby Nitric Acid Oxidation Patent Summary ...... 396 4.7 Recovery of Adipic Acid from Cyclohexanol/Cyclohexanone Nitric Acid Oxidation Patent Summary ...... 400 4.8 Treatment of Purge Stream from Adipic Acid Recovery Patent Summary ...... 401 4.9 Purification of Adipic Acid Patent Summary ...... 407 4.10 Adipic Acid from Cyclohexane by One-Step Molecular Oxygen Oxidation Patent Summary ...... 408 4.11 Adipic Acid from Cyclohexanol/Cyclohexanoneby Air Oxidation Patent Summary ...... 414 4.12 Cyclohexane to Adipic Acid by Direct Nitric Acid or Nitric Oxides Oxidation PatentSummary ...... 420 4.13 Adipic Acid by Oxidation with Ozone, Hydrogen Peroxide, Sulfuric Acid, or Other Compound Patent Summary ...... 422 4.14 Adipic Acid from Cyclohexane Design Bases and Assumptions ...... 47 4.15 Adipic Acid from Cyclohexane Stream Flows ...... 54 4.16 Adipic Acid from Cyclohexane Major Equipment ...... 58 4.17 Adipic Acid from Cyclohexane Utilities Summary ...... 62 4.18 Adipic Acid from Cyclohexane Waste Streams ...... 65

X TABLES

4.19 Adipic Acid from Cyclohexane Total Capital Investment ...... 73 4.20 Adipic Acid from Cyclohexane Production Costs ...... 76 4.21 Mipic Acid from Cyclohexane by Hydroperoxide Process Major Equipment...... 78 4.22 Adipic Acid from Cyclohexane by Hydroperoxide Process Production Costs ...... 79 4.23 Adipic Acid from Cyclohexane by Boric Acid Process Major Equipment...... 81 4.24 Adipic Acid from Cyclohexane by Boric Acid Process Production Costs ...... 83 4.25 Adipic Acid from Cyclohexane with Recovery of Acids from Aqueous Waste Major Equipment ...... 85 4.26 Adipic Acid from Cyclohexane with Recovery of Acids from Aqueous Waste Production Costs ...... 86 4.27 Adipic Acid from Cyclohexane, Low Recycle Process Major Equipment ...... 88 4.28 Adipic Acid from Cyclohexane, Low Recycle Process Production Costs ...... 89 4.29 Adipic Acid from Cyclohexane SummaryofCosts ...... 91

5.1 Cyclohexanol by Phenol Hydrogenation Patent Summary ...... 424 5.2 Cyclohexanol from Phenol by Hydrogenation

Design gases and Assumptions l l ...... l l . l l l 96 5.3 Cyclohexanol from Phenol by Hydrogenation Stream Flows ...... l . . 97 5.4 Cyclohexanol from Phenol by Hydrogenation Major Equipment ...... l . . . l l . . . l l l 98 5.5 Cyclohexanol from Phenol by Hydrogenation

Utilities Summary ...... l l . l l . . . l l l l l 99 5.6 Cyclohexanol from Phenol by Hydrogenation 1042 Total Capital Investment l l l l l l l l l l l l l l l l

Xi TABLES

5.7 Cyclohexanol from Phenol by Hydrogenation Production Costs ...... 105 5.8 Adipic Acid from Phenol via Cyclohexanol Total Capital Investment ...... 107 5.9 Mipic Acid from Phenol via cyclohexanol Production Costs ...... 108

6.1 Mipic Acid from Butadiene PatentSummary ...... 425 6.2 Mipic Acid from Butadiene

Design Bases and Assumptions l ...... 120 6.3 Mipic Acid from Butadiene Stream Flows ...... 127 6.4 Adipic Acid from Butadiene Major Equipment...... 131 6.5 Mipic Acid from Butadiene Utilitiee Summary ...... 135 6.6 Mipic Acid from Butadiene Total Capital Investment ...... 139 6.7 Mipic Acid from Butadiene Production Costs ...... 142

7.1 Mipic Acid by Biochemical Processes PatentSummary ...... 428 7.2 Mipic Acid from Cyclohexene Patent Summary ...... 429 7.3 Mipic Acid by Carbonylation of Ether PatentSummary ...... 431 7.4 Mipic Acid by Oxidation of Chlorocyclohexane PatentSummary ...... 432 7.5 Mipic Acid from Cyclohexylphenyl Ketone Patent Summary ...... 433 7.6 Miscellaneous Processes for Making Mipic Acid PatentSummary ...... 434

8.1 Miponitrile from Mipic Acid Patent Summary ...... 435

xii 8.2 Purification of Adiponitrile PatentSummary ...... 438 8.3 Hexamethylenediamine from Miponitrile by Hydrogenation Patent Summary ...... 441 8.4 Purification of Hexamethylenediamine PatentSummary ...... 444 8.5 HexamethylenediamineDirectly from Mipic Acid PatentSummary ...... 446 8.6 Hexamethylenediamine from Mipic Acid Design Bases and Assumptions ...... 155 8.7 Hexamethylenediamine from Mipic Acid StreamFlows ...... 160 8.8 Hexamethylenediamine from Mipic Acid Major Equipment...... 164 8.9 Hwxamethylenediamine from Mipic Acid Utilities Summary ...... 168 8.10 Hexamethylenediamine from Mipic Acid Total Capital Investment ...... 172 8.11 Hexamethylenediamine from Mipic Acid Production Costs ...... 174

9.1 Miponitrile from Butadiene via Dichlorobutene PatentSummary ...... 447 9.2 Hexamethylenediamine from Butadiene via Dichlorobutene and Dicyanobutene Design Bases and Aesumptions ...... 180 9.3 Hexamethylenediamine from Butadiene via Dichlorobutene and Dicyanobutene Stream Flows ...... 186 9.4 Hexamethylenediamine from Butadiene via Dichlorobutene and Dicyanobutene

Major Equipment...... l . . . . . 190 9.5 Hexamethylenediamine from Bu.tadienevia Dichlorobutene and Dicyanobutene Utilities Summary ...... 194

xiii TABLES

9.6 Hexamethylenediamine from Butadiene via Dichlorobutene and Dicyanobutene

Total Capital Investment ...... l . . 196 9.7 Hexamethylenediamine from Butadiene via Dichlorobutene and Dicyanobutene Production Costs ...... 198

10.1 Miponitrile from Butadiene by Hydrocyanation Summary of Du Pont Patents ...... 450 10.2 Miponitrile from Butadiene by Hydrocyanation Summary of Patents to Assignees Other than Du Pont . . . 452 10.3 Hexamethylenediamine from Butadiene via Eydrocyanation to Miponitrile Design Bases and Assumptions ...... 209 10.4 Hexamethylenediamine from Butadiene via Hydrocyanation to Miponitrile StreamFlows ...... 210 10.5 Hexamethylenediamine from Butadiene via Hydrocyanation to Adiponitrile MajorEquipment...... 212 10.6 Hexamethylenediamine from Butadiene via Hydrocyanation to Miponitrile Utilities Summary ...... 216 10.7 Hexamethylenediamine from Butadiene via Hydrocyanation to Miponitrile Total Capital Investment ...... 217 10.8 Hexamethylenediamine from Butadiene via Hydrocyanation to Miponitrile Production Costs ...... 220

11.1 Miponitrile by Electrohydrodimerieationof Acrylonitrile in Emulsion Summary of Asahi Chemical Patents ...... 454 11.2 Miponitrile by Electrohydrodimerizationof Acrylonitrile in an Undivided Cell - PatentSummary ...... 456 11.3 HNDA via ADN by Electrohydrodimerizationof Acrylonitrile in Solution Design Bases and Assumptions ...... 229 0 xiv TABLES

11.4 UMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Solution Stream Flows ...... 234 11.5 UMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Solution Major Equipment ...... 237 - 11.6 UMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Solution Utilities Summary ...... 241 11.7 DMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Solution Total Capital Investment ...... 243 11.8 DMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Solution Production Costs ...... 244 11.9 DMDA via Miponitrile by Electrohydrodimerizationof Acrylonitrile in Emulsion 0- Design Bases and Assumptions ...... 248 11.10 UMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Emulsion Stream Flows ...... 250 11.11 UMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Emulsion Major Equipment ...... 253 11.12 HMDA via AUN from Electrohydrodimerizationof Acrylonitrile in Emulsion Utilities Summary ...... 256 11.13 UMLIAvia ADN from Electrohydrodimerizationof Acrylonitrile in Emulsion a- Total Capital Investment ...... 259 11.14 UMDA via ADN from Electrohydrodimerizationof Acrylonitrile in Emulsion Production Costs ...... 260 11.15 UMUA via AUN by Electrohydrodimerizationof a- Acrylonitrile in An Undivided Cell Design Bases and Assumptions ...... l . . 263

0 xv TABLES

11.16 HMDA via ADN by Electrohydrodimerizationof Acrylonitrile in An Undivided Cell Stream Flows ...... 266 11.17 HMDA via ADN by Electrohydrodimerizationof Acrylonitrile in An Undivided Cell Major Equipment ...... 268 11.18 HKDA via ADN by Electrohydrodimerizationof Acrylonitrile in An Undivided Cell Utilities Summary ...... 271 11.19 BMDA via ADN by Electrohydrodimerizationof Acrylonitrile in An Undivided Cell Total Capital Investment ...... 275 11.20 HMDA via ADN by Electrohydrodimerizationof Acrylonitrile in An Undivided Cell Production Costs ...... 276

12.1 Adiponitrile from Acrylonitrile by Hydrodimerization with Sodium Amalgam Patent Summary ...... 458 12.2 Catalytic Dimerization of Acrylonitrile Patent Summary ...... 459 12.3 Adiponitrile by Other Processes Patent Summary ...... 464 12.4 Hexamethylenediamine from Caprolactam PatentSummary ...... 466 12.5 Hexamethylenediaminefrom Caprolactam Production Costs ...... 282 12.6 Hexamethylene from Diol, and Related Processes Patent Summary ...... 467 12.7 Hexamethylenediamineby the Diol Process Production Costs ...... 286 12.8 Hexamethylenediamine from Propylene and Ally1 Chloride Patent Summary ...... 470 12.9 Other Processes for Making Hexamethylenediamine Patent Summary ...... 471

xvi 13.1 Nylon Salt Preparation Patent Summary ...... 472 13.2 Nylon Salt Solutionin Aqueous Solution Design gases and Assumptions ...... 291 13.3 Nylon Salt in Aqueous Solution Stream Flows ...... 293 13.4 Nylon Salt in Aqueous Solution MajorEquipment ...... 294 13.5 Nylon Salt in Aqueous Solution Utilities Summary ...... 295 13.6 Nylon Salt in Aqueous Solution Total Capital Investment ...... 297 13.7 Nylon Salt in Aqueous Solution Production Costs ...... 298 13.8 Solid Nylon Salt from A Methanol Solution Design gases and Assumptions ...... 301 13.9 Solid Nylon Salt from A Methanol Solution Stream Flows ...... 302 13.10 Solid Nylon Salt from A Nethanol Solution MajorHquipment ...... 303 13.11 Solid Nylon Salt from A Methanol Solution

Utilities Summary...... l ...... 304 13.12 Solid Nylon Salt from A Methanol Solution Total Capital Investment ...... 306 13.13 Solid Nylon Salt from A Methanol Solution Production Costs ...... 307

14.1 Polycondeneation of Mipic Acid and Hexamethylenediamine to Nylon 66 PatentSummary ...... 473 14.2 Additives to Nylon 66 PatentSummary ...... 475 14.3 Nylon Resin from Nylon Salt Continuous Process Design gases and Assumptions ...... 316 14.4 Nylon 66 Resin from Nylon Salt Continuous Process Stream Flows ...... l l l ...... 317 TABLES

14.5 Nylon 66 Resin from Nylon Salt Continuous Process MajorEquipment...... 318 14.6 Nylon 66 Resin from Nylon Salt Standard Grade Utilities Summary ...... 322 14.7 Nylon 66 Resin from Nylon Salt Utilities Summary for Aftertreatment ...... 323 14.8 Nylon 66 L&sin from Nylon Salt Continuous Process Total Capital Investment ...... 327 14.9 ,Nylon 66 Eesin from Nylon Salt Standard Grade Production Costs ...... 330 14.10 Nylon 66 Resin from Nylon Salt Incremental Costs of Other Grades ...... 332 14.11 Nylon 66 Eesin from Nylon Salt Batch Process Major Equipment...... 335 14.12 Nylon 66 Resin from Nylon Salt Batch Process Utilities Summary ...... 336 14.13 Nylon 66 Resin from Nylon Salt Batch Process Total Capital Investment ...... 337 14.14 Nylon 66 Resin from Nylon Salt Batch Process Production Costs ...... 339

14sL5 Cost Features of Nylon Eesin from Waste Fiber . . . l . . 341

15.1 Additives to Fibers Including Nylon 66 PatentSumnary ...... 477 15.2 Spinning of Polyamides Including Nylon 66 Patent Summary ...... 478 15.3 Drawing, Texturing, and Crimping of Yarn Fibers Including Nylon 66 PatentSummary ...... 479 15.4 Nylon Fibers to Be Evaluated ...... 345 15.5 Carpet Staple from Nylon Salt Solution Total Capital Investment ...... 346 15.6 Carpet Staple from Nylon Salt Solution Production Costs ...... 348 15.7 Carpet Yarn from Nylon Salt Solution Total Capital Investment ...... 350

lwiii TABLES

15.8 Carpet Yarn from Nylon Salt Solution Production Costs ...... 352 15.9 Tire Cord from Nylon Salt Solution Total Capital Investment ...... 354 15.10 Tire Cord from Nylon Salt Solution Production Costs ...... 356 15.11 Textile Yarn from Nylon 66 Chips

Total Capital.Investment l ...... 358 15.12 Textile Yarn from Nylon 66 Chips Production Costs ...... 360 15.13 Hosiery Monofilament from Nylon 66 Chips

Total Capital Investment l ...... 362 15.14 Hosiery Monofilament from Nylon 66 Chips Production Costs ...... 364

A.1 Physical Properties of Selected Chemicals . . . . . l . . 369

XIX ILLUSTRATIONS

4.1 By-product Formation in Cyclohexane Oxidation to KA . . . 35 4.2 Reaction Mechanism for Nitric Acid Oxidation toMipicAcid...... 37 4.3 Mipic Acid from Cyclohexane Foldout...... 541 4.4 Boric Acid Recovery Foldout...... 547 4.5 Recovery of Acids from Aqueous Waste Foldout...... 549 4.6 Mipic Acid from Cyclohexane, Low Recycle Process Foldout...... 551

5.1 Cyclohexanol from Phenol Hydrogenation Foldout...... 553 5.2 Comparative Economics of the Phenol and Cyclohexane Processes for Making Mipic Acid ...... 110

6.1 Mipic Acid from Butadiene Foldout...... 557 6.2 Mipic Acid from Butadiene Block Flow Diagram ...... l ...... l 122

8.1 Hexamethylenediamine from Mipic Acid Foldout...... 561

9.1 Hexamethylenediamine from Butadiene via Dichlorobutene and Dicyanobutene Foldout...... 567

10.1 Hexamethylenediamine from Butadiene via Hydrocyanation to Miponitrile Foldout...... 573 10.2 IIMDAfrom Butadiene via Hydrogenation to Miponitrile Block Flow Diagram ...... 204

11.1 Concentration of Acrylonitrile in

Electrolyte on Cathode Surface . . l . . . . . l . . . l 227 11.2 HMDA via ADN by Electrohydrodimerieationof Acrylonitrile in Solution

Foldout . . l . l . l l l l . l l . l . . . l . l l m l l 577 ILLUSTRATIONS

11.3 HMDA via ADN by Electrohydrodimerizationof Acrylonitrile in Emulsion

Foldout ...... l ...... l . 583 11.4 HMDAvia ADNby Electrohydrodlmerization of Acrylonitrile in An Undivided Cell

Foldout l l l . l . l l l l l l l . l l l l . l l . l l l 587

12.1 Block Diagram of Diol Process for HMDA ...... 284 12.2 Block Diagram of Diol Process for BMDA andMipicAcid ...... 284

13.1 Manufacture of Nylon Salt Solution Foldout...... 589 13.2 Manufacture of Solid Nylon Salt Foldout...... 591

14.1 Nylon 66 l&sin by Continuous Process Foldout...... 593 14.2 Nylon 66 Eesin by Batch Process Foldout...... 597

A.1 Vapor Pressure of Cyclohexane, Cyclohexanol, and Cyclohexanone ...... 370 A.2 Vapor Pressure of Mipic Acid, Glutaric Acid, and Nitric Acid ...... 371 A.3 Solubility of Succinic Acid, Mipic Acid and Glutaric Acid in Water ...... 372 A.4 Vapor Pressure of Methyl Esters Relevant to the Recovery of Mipic Acid by Butadiene Process ...... 373 A.5 Vapor Pressure of Compounds Eelevant to the Manufacture of Miponitrile from Mipic Acid ...... 374 A.6 Vapor Pressure of Compounds Relevant to the Recovery of Miponitrile by the Butadiene Process . . . 375 A.7 Vapor Pressure of Compounds Eelevant to the Recovery of Miponitrile by Electrohydrodimerization of Acrylonitrile ...... 376 A.8 Vapor Pressure of lDlDAand 1,2-Diaminocyclohexane . . . . 377

xxii