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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
Recommended