Report No. 1-A

ISOCYANATES SUPPLEMENT A

PART I

By YEN-CHEN YEN

June. 1968

A private report. by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE

I

MENLO PARK, CALIFORNIA

c CHEMICAL ABBREVIATIONS USED IN THIS REPORT c

c / BTDI

DAD1

DDI@

DlvIF

DN?

HMDA

HDI

MCB

MD1 -\ c MDI, hydrogenated

ND1

ODCB

PACM

PAPI@

C

c I

c iv

PMPPA

PMPPI

TDA

TDI

TODI@

TVDI

XDA

XDI

Bitolylene diisocyanate

Dianisidine diisocyanate

A General Mills trade name for a complex diisocyanate made from dimer acid.

Dimethylformamide

Dinitrotoluene

Hexamethylaminediamine

Hexamethylene diisocyanate

Monochlorobenzene

Diphenylmethane diamine (methylene dianiline)

Diphenylmethane diisocyanate (methylene diphenylisocyanate)

4,4'-Diisocyanatodicyclohexylmethane

Naphthalene diisocyanate

Ortho-dichlorobenzene

Bis(p-aminocyclohexyl)methane

Polymethylene polyphenyl isocyanate', ;nu&;pjohn trade

Polymethylene polyphenylamine

Polymethylene polyphenyl isocyanate

Tolylenediamine

Tolylene diisocyanates

Bitolylene diisocyanate, an Upjohn trade name

Trans-vinylene diisocyanate

Xylylenediamine

Xylylene diisocyanate

CONTENTS

1 INTRODUCTION.......................... 1

3

2 SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3 INDUSTRY STATUS . . . . . . . . . . . . . , . . . . . . . , . . 19

4 CHEMISTRY OF AMINE PHOSGENATION . . . . . . , . . . . . . . . . 31

5 TOLUENEDIAMINE FROM DINITROTOLUENE . . . . . . . . . . . . . . . 39

Chemistry ........................... 39 Review of Processes ...................... 40 Process for DNT Purification .................. 47 Process Description ..................... 47 Process Discussion ...................... 53 Cost Estimates ........................ 53

Process Based on Du Pont Patents ................ 55 Process Description ..................... 55 Process Discussion ...................... 63 Cost Estimates ........................ 64

Process Based on Bayer and Mobay Patents ............ 69 Process Description ..................... 69 Process Discussion ...................... 74 Cost Estimates ........................ 74

Process Based.on an Olin Mathieson Patent ........... 79 Process Description ...................... 79 Process Discussion ...................... 84 Cost Estimates ........................ 85

6 TOLUENE DIISOCYANATE FRGM TOLUENEDIAMINE BY PHOSGENATION . . . . 89

Chemistry ........................... 89 Review of Processes ...................... 91 Process Based on Bayer and Mobay Patents ............ 110 Process Description ..................... 110 Process Discussion ...................... 119 Cost Estimates ......................... 121

Process Based on an Olin Mathieson Patent ........... 131 Process Description ..................... 131 Process Discussion ...................... 137 Cost Estimates ........................ 137

* 3

3

.-” _)

.-

.3

3

CONTENTS

7 VARIOUS COMMERCIAL FORMS OF TDI AND ITS MODIFICATIONS .....

Isomer Forms of TDI ...................... CrudeTDI ........................... TDI Adducts (Polyisocyanate from TDI) ............. Blocked Isocyanates ...................... Polymerized TDI (Dimer and Isocyanurate) ............. Encapsulated Isocyanate ....................

8 DIPHENYIMETHANE DIISOCYANATE, POLYMETHYLENE POLYPHENYL ISOCYANATE, AND REIATED ISOCYANATES ..............

Chemistry ........................... Formation of Diphenylmethanediamine and Polymethylene Polyphenylamine ....................... Phosgenation .........................

Review of Processes ...................... AmineFormation ....................... Phosgenation ......................... Purification and Stabilization ................ MD1 Adducts (Blocked MD1 and Polyisocyanate from MD11 .... Complex or Mixed Isocyanates .................

Polymethylene Polyphenyl Isocyanate by Hydrochloric Acid Condensation and Phosgenation ................. Process Description ..................... Process Discussion ...................... Cost Estimates ........................

Process for the Manufacture of 4,4'-MD1 ............ Process Description ..................... Process Discussion ...................... Cost Estimates ........................ Manufacturing MD1 Containing 90% of 4,4'-MD1 .........

Process for Making PMPPA Using Catalytic Amount of Acid .... Process for Making PMPPA Using Alumina as Catalyst .......

9 OTHER AROMATIC ISOCYANATES MADE BY PHOSGENATION ........

Review of Processes ...................... Phenyl Isocyanate by Gas Phosgenation ............. Process Description ..................... Process Discussion ...................... -

149

149 151 153 161 161 163

169

169

169 174 174 174 180 185 186 186

191 191 201 202

211 211 217 217 218 226 227

233

233 258 258 262

Cost Estimates . . . . . . . . . . . . . . . . . . . . . . . . 262

V

CONTENTS

9 (continued)

Para- and Ortho-Chloronitrobenzene from Chlorobenzene . . . . . Process Description , . . . . . . . . . . . . . . . . . . . . Process Discussion . . . . . . . . . . . . . . . . . . . . . . Cost Estimates ...................

Tri(4-Isocyanatophenyl) Thiophosphate from Para-Chloronitrobenzene ........... ; ... Chemistry ..................... Process Description ................ Process Discussion ................. Cost Estimates ...................

Dianisidine Diisocyanate from Ortho-Chloronitrobenzene Chemistry ..................... Process Description ................ Process Discussion ................. Cost Estimates ...................

Naphthalene Diisocyanate ............... 3,3'-Bitolylene-4,4cDiisocyanate ........... Triphenylmethane Triisocyanate ............

. . . . .

265 265 273 274

. . . . . 279

. . . . . 279

. . . . . 279

. . . . . 297

. . . . . 297

. . . . . 305

. . . . . 305

. . . . . 307

. . . . . 323

. . . . . 323

. . . . . 331

. . . . . 336

. . . . . 339

vi

ILLUSTRATIONS

5.1

5.2

5.3

5.4

6.1

6.2

6.3

6.4

6.5

7.1 Polyisocyanate from TDI . . . . . . . . . . . . . . . . . . . 159

8.1 Relationship of Composition of Condensation Product with the Ratio of Aniline to Formaldehyde . . . . . . . . . . . . 172

8.2 PMPPI by Hydrochloric Acid Condensation and Phosgenation . . 195

8..3 Production Costs of PMPPI at Various Production Scales and Stream Factors . . . . . . . . . . . . . . . . . . . . . . . 209

8.4

8.5

8.6

Purification of DNT . . . . . . . . . . . . . . . . . . . . . 49

TDA from DNT: Process Based on Du Pont Patents . . . . . . . 59

TDA from DNT: Process Based on Bayer and Mobay Patents . . . 71

TM from DNT: Process Based on an Olin Mathieson Patent . , 81

TDI from TDA by Phosgenation Based on Bayer and Mobay Patents........................... 113

TDI from Toluene: Hydrogenation and Phosgenation Based on Bayer and Mobay Patents Variation of Production Cost with Plant Capacity . . . . . . 129

Dependence of Production Cost of TDI on the Unit Cost of Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . 130

TDI from TDA by Phosgenation Based on an Olin Mathieson Patent . . . . . . . . . . . . . . . . . . . . . . . . . . . 133

TDI from Toluene: Hydrogenation and Phosgenation Based on Olin Mathieson Patents Variation of Production Cost with Plant Capacity . . . . . . 147

Effect of Unit Prices of Raw Materials on Production Cost OfPMPPI . . . . . . . . . . . . . . . . . . . . . . . . . . 210

Production Costs of MD1 at Various Production Scales and Stream Factors . . . . . . . . . . . . . . . . . . . . . . . 225

Polymethylene Polyphenylamine by Alumina-Silica Catalyst Condensation Process . . . . . . . . . . . . . . . . . . . . 229

Vii

ILLUSTRATIONS

9.1 Phenyl Isocyanate by Gas Phosgenation . . . . . . . . . . . . 259

9.2 Para- and Ortho-Chloronitrobenzene from Chlorobenzene . . . . 269

9.3 Tri(4-Isocyanatophenyl) Thiophosphate from Para-Chloronitrobenzene . . . . . . . . . . . . -. . . . . . . 285 0

9.4 Dianisidine Diisocyanate from Ortho-Chloronitrobenzene . . . 311

Viii

TABLES

2.1

2.2

2.3

2.4

2.5

3.1

3.2

3.3

5.1

5.2 Patents on Purification of Toluenediamine . . .

5.3 Purification of DNT

5.4 Purification of DNT

5.5 Purification of DNT

5.6

5.7

5.8

Summary of Costs of TDI Production . . . . . . . . . . . . . .

Summary of Costs of PMPPI and MD1 Production . . . . . . . . .

Summary of Costs of Various Isocyanates . . . . . . . . . . .

Comparison of Various Phosgenation Processes for Manufacture of Isocyanates . . . . . . . . . . . . . . . . . . . . . . . .

Comparison of the Carbon Monoxide Process and the Phosgenation Process for Manufacture of Phenyl Isocyanate . . . . . . . . .

Isocyanates Produced in the United States . . . . . . . . . .

Plant Capacity for Isocyanates in the United States . . . , .

Plant Capacity for Isocyanates in Countries Outside the United States . . . . . . . . . . . . . . . . . . . . . . . .

Patents on Processes for Producing TJlA by Reduction of DNT with Hydrogen . . . . . . . . . . . . . . . . .

Major Process Equipment and Utilities Summary .

StreamFlows. . . . . . . . . . . . . . . . . .

Process Unit and Utilities Investment . . . . .

TDA from DNT: Process Based on Iha Pont Patents Major Process Equipment and Utilities Summary .

TDA from DNT: Process Based on Du Pont Patents Stream Flows . , . . . . . . . . . . . . . . . .

TM from DNT: Process Based on Du Pont Patents Process Unit and Utilities Investment . . . . .

.......

.......

.......

.......

.......

.......

.......

.......

5

6

9

15

18

25

27

29

41

45

49

51

54

57

61

65

iX

5.9

5.10

5.11

5.12

5.13

5.14

5.15

5.16

5.17

6.1

6.2

6.3

6.4

6.5

6.6

TDA from DNT: Process Based on Du Pont Patents Direct Operating Costs ....................

TM from DNT: Process Based on Bayer and Mobay Patents Major Process Equipment and Utilities Summary ........

TDA from DNT: Process Based on Bayer and Mobay'Patents StreamFlows .........................

TM from DNT: Process Based on Bayer and Mobay Patents Process Unit and Utilities Investment ............

TIN from DNT: Process Based on Bayer and Mobay Patents Direct Operating Costs ....................

TDA from DNT: Process Based on an Olin Mathieson Patent Major Process Equipment and Utilities Summary ........

TIN from DNT: Process Based on an Olin Mathieson Patent StreamFlows .........................

TDA from DNT: Process Based on an Olin Mathieson Patent Process Unit and Utilities Investment ............

TDA from DNT: Process Based on Olin Mathieson Patents Direct Operating Costs ....................

Patents on Phosgenation of TDA to TDI ............

Patents on Phosgenation of TDA Salt to TDI ..........

Patents Relating to Phosgene Recovery and Waste Gas Treatment juring Phosgenation .....................

Patents on Purification of Isocyanates by Reducing Their Hydrolyzable Chlorine Content ................

Patents Relating to the Distillation of Crude TDI and Treatment of the Distillation Residue ............

Patents on Stabilization of Isocyanates ...........

67

71

0

73

76

77

81

0 a3

86

87

93

99

103 0

104

106 0

107

X

TABLES

6.7

6.8

6.9

6.10

6.11

6.12

6.13

6.14

6.15

6.16

7.1

7.2

7.3

7.4

TDI from TDA by Phosgenation Based on Bayer and Mobay Patents Major Process -Equipment and Utilities Summary . . . . , . . . 113

TDI from TDA by Phosgenation Based on Bayer and Mobay Patents StreamFlows......................... 117

TDI from TDA by Phosgenation Based on Bayer and Mobay Patents Process Unit and Utilities Investment . . . . . . . . . . . . 123

TDI from Toluene. Hydrogenation and Phosgenation Based on Bayer and Mobay Patents Total Capital Investment . . . . . . . . . . . . . . . . . . . 125

TDI from Toluene: Hydrogenation and Phosgenation Based on Bayer and Mobay Patents Production Costs . . . . . . . . . . . . . . . . . . . . . . . 127

TDI from TIN by Phosgenation Based on an Olin Mathieson Patent Major Process Equipment and Utilities Summary . . . . . . . , 133

TDI from TDA by Phosgenation Based on an Olin Mathieson Patent StreamFlows......................... 135

TDI from TDA by Phosgenation Based on an Olin Mathieson Patent Process Unit and Utilities Investment . . . . . . . . . . . . 141

TDI from Toluene: Hydrogenation and Phosgenation Based on Olin Mathieson Patents Total Capital Investment . . . . . . . . . . . . . . . . '. . . 143

TDI from Toluene: Hydrogenation and Phosgenation Based on Olin Mathieson Patents Production Costs . . . . . . . . . . . . . . . . . . . . . . 145

Patents on the Separation of TDI Isomers or on Changing the Isomer Ratio . . . . . . . . . . . . . . . . . . . . . . . . . 150

Patents Related to the Use of Crude TDI . . . . . . . . . , . 152

Patents on Blocked TDI and Polyisocyanates from TDI . . . . . 155

Polyisocyanate from TDI Major Process Equipment List . . . . . . . . . . . . . . . . . 159

Xi

TABLES

7.5

7.6

8.1

8.2

8.3

8.4

8.5

8.6

8.7

8.8

8.9

8.10

8.11

8.12

8.13

Patents on Isocyanates and Dimers from TDI ..........

Patents on Encapsulated Isocyanates .............

Patents on the Condensation of Aniline and Formaldehyde to Form Diaminodiphenylmethane or a Polyamine .........

Patents on the Preparation of MD1 and PMPPI from Amine by Phosgenation .......................

Patents on the Preparation of MD1 and PMPPI from Amine Salt by Phosgenation .......................

Patents on the Purification and Stabilization of MD1 and PMPPI ............................

Patents on Polyisocyanates from MD1 or PMPPI .........

PMPPI by Hydrochloric Acid Condensation and Phosgenation Major Process Equipment and Utilities Summary ........

PMPPI by Hydrochloric Acid Condensation and Phosgenation StreamFlows .........................

PMPPI by Hydrochloric Acid Condensation and Phosgenation Process Unit and Utilities Investment ............

PMPPI by Hydrochloric Acid Condensation and Phosgenation Total Capital Investment ...................

PMPPI by Hydrochloric Acid Condensation and Phosgenation Production Costs .......................

MD1 by Hydrochloric Acid Condensation and Phosgenation Major Process Equipment and Utilities Summary ........

MD1 by Hydrochloric Acid Condensation and Phosgenation StreamFlows .........................

MD1 by Hydrochloric Acid Condensation and Phosgenation

0 165

167

175 0

181

183

187

189

0 195

199

203

205

207 0

212

215 0

Process Unit and Utilities Investment . . . . . . . . . . . . 219

xii

TABLES

-

0

8.14

8.15

8.16

8.17

8.18

9.1

9.2

9.3

9.4

9.5

9.6

9.7

9.8

9.9

MD1 by Hydrochloric Acid Condensation and Phosgenation Total Capital Investment . . . . , . . . . . . . . . . . . . 221

MD1 by Hydrochloric Acid Condensation and Phosgenation Production Costs . . . . . , . . . . . . . . . . . . . . . . 223

Polymethylene Polyphenylamine by Alumina- Silica Catalyst Condensation Major Process Equipment and Utilities Summary . . . . . . . 229

Polymethylene Polyphenylamine by Alumina-Silica Catalyst Condensation StreamFlows........................ 231

Polymethylene Polyphenylamine by Alumina-Silica Catalyst Condensation Process Unit and Utilities Investment . , . . . . . . . . . 232

Patents on Preparation of Aromatic Isocyanates Other Than TDI and MD1 by Liquid-Phase Phosgenation Processes . . . . . 235

Patents on Halogen-Containing Aromatic Isocyanates Made by Phosgenation of Haloamines . . . . . . . . . . . . . . . . . 241

Patents on Aromatic Isocyanates Containing Sulfonyl Groups Produced by Phosgenation . . . . . . . . . . . . . , . . . . 243

Patents on Aromatic Isocyanates Containing Phosphorus or Silicon Made by Phosgenation . . . . . . . . . . . . . . . . 245

Patents on Halogenation of Isocyanates . . . . . . . , . . . 251

Patents on Preparation of Aromatic and Aliphatic Isocyanates by Gas-Phase Phosgenation , , , . . . . , . . . . . . . . . 255

Phenyl Isocyanate by Gas Phosgenation Major Process Equipment and Utilities Summary . . . . . . . 259

Phenyl Isocyanate by Gas Phosgenation StreamFlows........................ 261

Phenyl Isocyanate by Gas Phosgenation Process Unit and Utilities Investment and Total Capital Investment . . . . . . . . . . . . . . . . . . . . . . . . . 263

xiii

TABLES

9.10

9.11

9.12

9.13

9.14

9.15

9.16

9.17

9.18

9.19

9.20

9.21

9.22

Phenyl Isocyanate by Gas Phosgenation Production Costs . . . , . . , . . . . . . . . . . . . . . . 264

Para- and Ortho-Chloronitrobenzenes from Chlorobenzene Major Process Equipment and Utilities Summary . . , . . . , 267

Para- and Ortho-Chloronitrobenzenes from Chlorobenzene StreamFlows........................ 271

Para- and Ortho-Chloronitrobenzene from Chlorobenzene Process Unit and Utilities Investment . . . . . . . . . . , 275

Para- and Ortho-Chloronitrobenzene from Chlorobenzene Total Capital Investment . . . . . . . . . . . . . . . . . . 276

Para- and Ortho-Chloronitrobenzene from Chlorobenzene Production Costs . . . . . . . . . . . . . . . . . . . . . . 277

Tri(4-Isocyanatophenyl) Para-Chloronitrobenzene Major Process Equipment

Tri(4-Isocyanatophenyl) Para-Chloronitrobenzene

Thiophosphate

and Utilities

Thiophosphate

from

Summary . . . . . . . 285

from

StreamFlows........................ 291

Tri(4-Isocyanatophenyl) Thiophosphate from Para-Chloronitrobenzene Process Unit and Utilities Investment . . . . . . . . . . . 299

Tri(4-Isocyanatophenyl) Thiophosphate from Para-Chloronitrobenzene Total Capital Investment . . . . . . . . . . . . . . . . . . 301

Tri(4-Isocyanatophenyl) Thiophosphate from Para-Chloronitrobenzene Production Costs . . . . . . . . . . . . . . . . . . . . . . 303

Dianisidine Diisocyanate from Ortho-Chloronitrobenzene Major Process Equipment and Utilities Summary . . . . . . . 310

Dianisidine Diisocyanate from Ortho-Chloronitrobenzene StreamFlows. . . . . . . . . . . . . . . . . . . . . . . . . 317

0

0

0. xiv

TABLES

9.23

9.24

9.25

9.26

9.27

9.28

9.29

9.30

Dianisidine Diisocyanate from Ortho-Chloronitrobenzene Process Unit and Utilities Investment . . . . . . , . . . . 325

Dianisidine Diisocyanate from Ortho-Chloronitrobenzene Total Capital Investment . . . . . . . . . . . . . . . . . . 327

Dianisidine Diisocyanate from Ortho-Chloronitrobenzene Production Costs . . . . . . . . . . . . . . . . . . . . . . 329

Naphthalene Diisocyanate from Naphthalene Total Capital Investment . . . . . . . . . . . . . . . . . . 334

Naphthalene Diisocyanate from Naphthalene Production Cost . . . . , . . . . . . . . . . . . . . . . . 335

Bitolylene Diisocyanate from Toluene Total Capital Investment . . . . . . . . . . . . . . . . . . 337

Bitolylene Diisocyanate from Toluene Production Costs . . . . . . . . . . . . . . . . . . . . . . 338

Triphenylmethane Triisocyanate Manufacture Production Costs , . . . . . . . . . . . . . . . . . . . . . 340

xv