Report No. 57A Supplement

POLYVINYL ACETATE AND

POLYVINYL ALCOHOL

by YU-REN CHIN

September 1976

a A private report by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE I

MENLO PARK, CALIFORNIA

CONTENTS

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

2 SUMMARY.............................

3 INDUSTRY STATUS. ........................

Polyvinyl Acetate ....................... Polyvinyl Alcohol Polyvinyl Butyral an: Poiy$iyi Fokal', ..........................

4 POLYVINYL ACETATE BY EMULSION POLYMERIZATION ..........

Chemistry Review of Pa;eiti

........................ .......................

Process Description ...................... Raw Material Storage and Purification ............ Polymerization and Product Storage ..............

Process Discussion ....................... Cost Estimates ......................... Capital Costs ........................ Production Costs .......................

5 POLYVINYL ACETATE BY OTHER POLYMERIZATION PROCESSES ......

Review of Processes Solution Polymerizat;o;l

.................... ...................

Suspension Polymerization .................. Bulk Polymerization .....................

Process Descriptions ...................... Solution Polymerization ...................

Raw Material Storage and Purification ........... Polymerization ....................... Monomer and Solvent Recovery ................ Finishing and Bulk Handling ................

Suspension Polymerization ................... Raw Material Storage and Purification ........... Polymerization ....................... Product Dewatering and Drying ............... Bulk Handling .......................

Process Discussion ....................... Cost Estimates ......................... Solution Polymerization ................... Capital Costs ....................... Production Costs ......................

Suspension Polymerization .................. Capital Costs ....................... Production Costs ......................

Vii

2

3

11 20 25

27

27 29 29 35 38 41 41 41 42

51

51 51 54 55 56 56 57 57 58 58 64 65 65 66 66 71 73 73 73 74 84

i::

CONTENTS

6 POLYVINYL ALCOHOL . . . . . . . . . . . . . . . . . . . . . . : 95

General . . . . . . . . . . . . . . . . ............ 95

Chemistry . . . . . . . . . . . . . . . ............ 96

Review of Processes . . . . . . . . . . ............ 100

Polymerization of Vinyl Acetate . . . ............ 100

Hydrolysis of Polyvinyl Acetate . . . ............ 101

Process Description . . . . . . . . . . ............ 106

Raw Material Storage and Purification ............ 108

Polymerization and Hydrolysis . . . . ............ 108

Solvent Separation and Product Drying ............ 109

Bulk Handling . . . . . . . . . . . . ............ 109

Solvent and By-Product Recovery . . . ............ 109

Process Discussion . . . . . . . . . . ............ 117

Cost Estimates . . . . . . . . . . . . ............ 118 Capital Costs . . . . . . . . . . . . ............ 118

Production Costs . . . . . . . . . . ............ 119

7 POLYVINYL BUTYRAL AND POLYVINYL FORMAL . . . . . . . . . . . . 131

Chemistry ........................... 131

Review of Processes ...................... 133

Acetalization Processes ................... 133

Work-up Processes ...................... 145

Process Description ...................... 146

Raw Material Storage and Purification ............ 147

Polymerization, Hydrolysis, and Condensation ........ 148

Product Washing and Drying ................. 148

Bulk Handling ........................ 150

Solvent and By-Product Recovery ............... 150

Process Discussion ...................... 157

Cost Estimates ........................ 158

Capital Costs ........................ 158

Production Costs ...................... 158

8 ETHYLENE-VINYL ACETATE AND ETHYLENE-VINYL ALCOHOL COPOLYMERS . . 169

Review of Patents ....................... 169

Ethylene-Vinyl Acetate Copolymer .............. 169

Ethylene-Vinyl Alcohol Copolymer .............. 180

Process Description ...................... 184

Baw Material Storage and Purification ............ 185

Polymerization and Product Storage ............. 186

Process Discussion ...................... 193

Costs Estimates ........................ 194

Capital Costs ........................ 194

Production Costs ...................... 195

Viii

CONTENTS

APPENDIX A DESIGN AND COSTS BASIS . . . . . . . . . . . . . . . . 207

APPENDIX B COMMERCIAL POLYVINYL ACETATE, POLYVINYL ALCOHOL, POLYVINYL BUTYRAL, POLYVINYL FORMAL, AND ETHYLENE- VINYLACETATE COPOLYMER.. . . , . . . . . . . . . . . . 211

APPENDIX C MODIFIED POLYVINYL ACETATE, POLYVINYL ALCOHOL, AND ETHYLENE-VINYL ACETATE COPOLYMERS . . . . . . . . . . 223

APPENDIX D TREATMENT AND APPLICATION OF POLYVINYL ALCOHOL AND POLYVINYL BUTYRAL . . . . . . . . . . . . . . . . . . 239

CITED REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . 269

PATENT REFERENCES BY COMPANY . . . . . . . . . . . . . . . . . . . 285

iX

ILLUSTRATIONS

4.1

4.2

4.3

4.4

5.1

5.2

5.3

5.4

5.5

5.6

5.7

5.8

6.1

Polyvinyl Acetate by Emulsion Polymerization Flowsheet . . . . . . . . . . . . . . . . . . . . . . . . . .

Polyvinyl Acetate by Emulsion Polymerization Effect of Plant Capacity on Total Fixed Capital . . . . . . .

Polyvinyl Acetate by Emulsion Polymerization Effect of VAM Price on Production Cost . . . . . . . . . . .

Polyvinyl Acetate by Emulsion Polymerization Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . . .

Polyvinyl Acetate by Solution Polymerization Flowsheet . . . . . . . . . . . . . . . . . . . . . . . . . .

Polyvinyl Acetate by Suspension Polymerization Flowsheet . . . . . . . . . . . . . . . . . . . . . . . . . .

Polyvinyl Acetate by Solution Polymerization Effect of Plant Capacity on Total Fixed Capital . . . . . . .

Polyvinyl Acetate by Solution Polymerization Effect of VAM Price on Production Cost . . . . . . . . . . .

Polyvinyl Acetate by Solution Polymerization Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . . .

Polyvinyl Acetate by Suspension Polymerization Effect of Plant Capacity on Total Fixed Capital . . . . . . .

Polyvinyl Acetate by Suspension Polymerization Effect of VAM Price on Production Cost . . . . . . . . . . .

Polyvinyl Acetate by Suspension Polymerization Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . . .

291

44

48

49

295

299

79

82

83

89

92

93

Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Flowsheet . . . . . . . . . . . . . . . . . . . . . . . . . . 303

Xi

ILLUSTRATIONS

4.2 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Effect of Plant Capacity on Total Fixed Capital . . . . . . . 121

6.3 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Effect of VAM Price on Production Cost . . . . . . . . . . . 125

6.4 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . . . 126

6.5 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Effect of Acetic Acid Credit on Total Capital Investment and NetProductionCost . . . . . . . . . . . . . . . . . . . . 127

7.1 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Butyraldehyde Flowsheet . . . . . . . . . . . . . . . . . . . . . . . . . . 309

7.2 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Butyraldehyde Effect of Plant Capacity on Total Fixed Capital . . . . . . . 163

7.3 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Butyraldehyde Effect of VAM Price on Production Cost . . . . . . . . . . . 166

7.4 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Butyraldehyde Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . . 167

7.5 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Butyraldehyde Effect of Acetic Acid Credit on Total Capital Investment and Net Production Cost . . . . . . . . . . . . . . . . . . . . 168

8.1 Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Flowsheet . . . . . . . . . . . . . . . . . . . . . . . . . . 317

8.2 Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Effect of Plant Capacity on Total Fixed Capital . . . . . . . 198

Xii

ILLUSTRATIONS

8.3 Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Effect of VAM Price on Production Cost . . . . . . . . . . . 202

8.4 Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . . 203

8.5 Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Effect of Ethylene Content on Production Cost . . . . . . . 204

Xiii

TABLES

2.1 Manufacture of Polyvinyl Acetate Summary of Process Conditions . . . . . . . . . . . . . . . . 4

2.2 Manufacture of Polyvinyl Acetate Summary of Process Economics . . . . . . . . . . . . . . . . 5

2.3 Manufacture of Polyvinyl Alcohol, Pdlyvinyl Butyral, and Ethylene-Vinyl Acetate Sunmary of Process Conditions . . . . . . . . . . . . . . . . 8

2.4 Manufacture of Polyvinyl Alcohol, Polyvinyl Butyral, and Ethylene-Vinyl Acetate Summary of Process Economics . . . . . . . . . . . . . . . . 9

3.1 Polyvinyl Acetate Plants United States . . . . . . . . . . . . . . . . . . . . . . . . 13

3.2 Polyvinyl Acetate Plants Western Europe . . . . . . . . . . . . . . . . . . . . . . . 14

3.3 Polyvinyl Acetate Plants Other Americas, Africa, Asia, Oceania, and Eastern Europe . . 16

3.4 Polyvinyl Alcohol Plants Asia and Europe . . . . . . . . . . . . . . . . . . . . . . . 21

3.5 Polyvinyl Alcohol Plants The Americas . . . . . . . . . . . . . . . . . . . . . . . . 22

4.1 Polyvinyl Acetate by Emulsion Polymerization Patent Summary , . . . . . . . . . . . . . . . . . . . . . . 30

4.2 Polyvinyl Acetate by Emulsion Polymerization Major Equipment and Utilities Summary . . . . , . . , . . . . 36

4.3 Polyvinyl Acetate by Emulsion Polymerization Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . 39

4.4 Polyvinyl Acetate by Emulsion Polymerization Waste Streams Summary . . . . , . . . . . . . . . . . . . . . 40

4.5 Polyvinyl Acetate by Emulsion Polymerization Total Capital Investment . . . . . . . . . . . . . . . . . . 43

xv

TABLES

4.6 Polyvinyl Acetate by Emulsion Polymerization Production Costs . . . . . . . . . . . . . . . . . . . . .

5.1 Polyvinyl Acetate by Solution Polymerization PatentSurrPnary . . . . . . . . . . . . . . . . . . . . . .

5.2 Polyvinyl Acetate by Solution Polymerization Major Equipment and Utilities Sunxnary . . . . . . . . . .

5.3 Polyvinyl Acetate by Solution Polymerization Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

5.4 Polyvinyl Acetate by Solution Polymerization Waste Streams Sunznary . . . . . . . . . . . . . . . . . .

5.5 Polyvinyl Acetate by Suspension Polymerization Major Equipment and Utilities Summary . . . . . . . . . .

5.6 Polyvinyl Acetate by Suspension Polymerization Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

5.7 Polyvinyl Acetate by Suspension Polymerization Waste Streams Suuxnary . . . . . . . . . . . . . . . . . .

5.8 Polyvinyl Acetate by Solution Polymerization Total Capital Investment . . . . . . . . . . . . . . . . .

5.9 Polyvinyl Acetate by Solution Polymerization Production Costs . . . . . . . . . . . . . . . . . . . . .

5.10 Polyvinyl Acetate by Suspension Polymerization Total Capital Investment . . . . . . . . . . . . . . . . .

5.11 Polyvinyl Acetate by Suspension Polymerization Production Costs . . . . . . . . . . . . . . . . . . . . .

6.1 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate PatentSunznary . . . . . . . . . . . . . . . . . . . . . .

,

6.2 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Major Equipment and Utilities Summary . . . . . . . . . .

4.3 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

46

52

59

62

63

67

69

70

76

80

86

90

102

111

114

xvi

TABLES

0

0 -

0

6.4 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Waste Streams Sunnnary . . . . . . . . . . . . . . . . . . .

6.5 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Total Capital Investment . . . . . . . . . . . . . . . . .

6.6 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Using WAC as Starting Material Total Capital Investment . . . . . . . . . . . . . . . . .

6.7 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Production Costs . . . . . . . . . . . . . . . . . . . . .

6.8 Polyvinyl Alcohol by Hydrolysis of Polyvinyl Acetate Using PVAc as Starting Material Production Costs . . . . . . . . . . . . . . . . . . . . .

7.1 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Bu tyra ldehyde PatentSummary . . . . . . . . . . . . . . . . . . . . . .

7.2 Polyvinyl Formal by Condensation of Polyvinyl Alcohol with Formaldehyde Patent Summary . . . . . . . . . . . . . . . . . . . . . .

7.3 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Bu tyra ldehyde

Major Equipment and Utilities Surwnary . . . . . . . . . . .

7.4 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Bu tyra ldehyde Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .

7.5 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Bu tyra ldehyde

Waste Streams Sutrnnary . . . . . . . . . . . . . . . . . . . 156

7.6 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Bu tyra ldehyde Total Capital Investment . . . . . . . . . . . . . . . . .

7.7 Polyvinyl Butyral by Condensation of Polyvinyl Alcohol with Bu tyra ldehyde Production Costs . . . . . . . . . . . . . . . . . . . . .

116

122

124

128

130

134

140

151

154

160

164

xvii

TABLES

8.1

8.2

8.3

8.4

8.5

8.6

8.7

8.8

8.9

B-1

B.2

B.3

B.4

B-5

B-6

B.7

c-1

Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization PatentSummary . . . . . . . . . . . . . . . . . . . . . .

Ethylene-Vinyl Alcohol Copolymer by Hydrolysis of Ethylene- Vinyl Acetate Copolymer PatentSummary . . . . . . . . . . . . . . . . . . . . . .

Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Major Equipment and Utilities Sunznary . . . . . . . . . .

Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Sumry of Waste Streams . . . . . . . . . . . . . . . . .

Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Total Capital Investment . . . . . . . . . . . . . . . . .

Ethylene-Vinyl Acetate Resin by Emulsion Polymerization Total Capital Investment . . . . . . . . . . . . . . . . .

Ethylene-Vinyl Acetate Copolymer by Emulsion Polymerization Production Costs . . . . . . . . . . . . . . . . . . . . .

Ethylene-Vinyl Acetate Resin by Emulsion Polymerization Production Costs . . . . . . . . . . . . . . . . . . . . .

Commercial Polyvinyl Acetate . . . . . . . . . . . . . . .

Properties of Polyvinyl Acetate . . . . . . . . . . . . .

Cocznercial Polyvinyl Alcohol . . . . . . . . . . . . . . .

Classification of Polyvinyl Alcohol . . . . . . . . . . .

Cozznercial Polyvinyl Butyral and Polyvinyl Formal . . . .

Properties of Polyvinyl Butyrals . . . . . . . . . . . . .

Properties of Polyvinyl Formals . . . . . . . . . . . . .

Modified Polyvinyl Acetate PatentSumna7.y . . . . . . . . . . . . . . . . . . . . . .

I

170

182

188

191

192

197

199

200

205

212

213

215

216

217

218

220

224

xviii

TABLES

c.2 Modified Polyvinyl Alcohol PatentSurrrnary . . . . . . . . . . . . . . . . . . . . . . 228

c.3 Modified Ethylene-Vinyl Acetate Copolymer PatentSummary . . . . . . . . . . . . . . . . . . . . . . 232

D.1 Treatment of Polyvinyl Alcohol Fiber PatentSusunary . . . . . . . . . . . . . . . . . . . . . . 240

D.2 Treatment of Polyvinyl Alcohol Film PatentSutmnary . . . . . . . . . . . . . . . . . . . . . . 248

D.3 Applications of Polyvinyl Alcohol PatentSummary . . . . . . . . . . . . . . . . . . . . . . 254

D.4 Applications of Polyvinyl Butyral PatentSummary . . . . . . . . . . . . . . . . . . . . . . 259

XIX