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Ad+=--= PROCESS &-==+ ECONOMICS ECONOMICS
--AA‘. --AA‘. PROGRAM PROGRAM SRI INTERNATIONAL SRI INTERNATIONAL
Abstract
Process Economics Program Report No. 124
ION EXCHANGE RESINS
(December 1979)
Menlo Park, California
94025
Ion exchange resins are produced in most major industrial coun-
tries of the world and are widely used for water treatment, chemical
processing, sugar refining , and for many other purposes. The most
commonly used synthetic ion exchange resins are made from a copolymer
of styrene and divinylbenzene.
This report presents technical and economic evaluations for the
manufacture of typical ion exchange resins. It includes estimates of
the world production capacities for all major kinds of resins, relative
amounts of the various functional types produced, and consumption
patterns for the United States and Europe.
Detailed process descriptions and cost estimates are presented for
anion and cation resins based on poly(styrene-divinylbenzene) and on
acrylic resins.
PEP '77 GER
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Report No. 124
ION EXCHANGE RESINS
by GRANT E. RUSSELL
December 1979
A private report by the
PROCESS ECONOMICS PROGRAM
Menlo Park, California 94025
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For detailed marketing data and information, the reader is
referred to one of the SRI programs specializing in marketing
research. The CHEMICAL ECONOMICS HANDBOOK Program covers
most major chemicalsPhnd chemical products produced in the
United States and the WORLD PETROCHEMICALS Program covers
major hydrocarbons and their derivatives on a worldwide basis.
In addition, the SRI DIREC'COKY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company, prod-
uct, and plant for the United States and Western Europe.
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CONTENTS
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1 INTRODUCTION. . . . . . . . . . . . . . . . . . . . . .
2 SUMMARY . . . . . . . . . . . . . . . . . . . . . . . .
3 INDUSTRY STATUS . . . . . . . . . . . . . . . . . . . . 15
4 CHEMISTRY .......................
ThePolymerMatrix ................... The Poly(styrene-DVB) Matrix .............. Cation Exchangers ................... Strong-Acid Resins ................... Weak-Acid Resins .................... Anion Exchangers .................... Strong-Base Resins ................... Weak-Base Resins. ................... Adsorbent Resins .................... Chelating or Ion-Specific Resins ............
5 REVIEW OF PROCESSES . . . . . . . . . . . . . . . . . . 55
6 MANUFACTURE OF POLY(STYRENE-DVB) BEADS .........
Process Description--Polymerization of Styrene-DVB for Gel-Type Ion Exchange Beads ......
Process Description--Polymerization of Styrene DVB for Macroporous Ion Exchange Beads ............ Process Discussion ................... Cost Estimates. ....................
171
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MANUFACTURE OF POLY(STYRENE-DVB) STRONG-ACID CATION EXCHANGERS . . . . . . . . . . . . . . . . . . . . . .
Process Descriptions .................. Process Discussion ................... Cost Estimates. ....................
CHLOROMETHYLATION OF POLY(STYRENE-DVB) BEADS ...... 217
Process Description .................. 218 Process Discussion ................... 225 Cost Estimates ..................... 228
AMINATION OF CHLOROMETHYLATED POLY(STYRENE-DVB) . . . . 229
Process Description . . . . . . . . . . . . . . . . . . 229 Cost Estimates. . . . . . . . . . . . . . . . . . . . . 241
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32 35 37 37 40 41 45 46 49 50
173
179 184 186
195
196 205 207
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CONTENTS
10 MANUFACTURE OF POLY(METHYL ACRYLATE-DVB) BEADS ..... 255
Process Description .................. 256 Process Discussion ................... 263 CostEstimates ..................... 264
11 MANUFACTURE OF WEAK-ACID ACRYLIC ION EXCHANGERS . . . . 269
Process Discussion . . . . . . . . . . . . . . . . . . . 277 Cost Estimates. . . . . . . . . . . . . . . . . . . . . 277
12 MANUFACTURE OF WEAK-BASE ACRYLIC RESINS ........ 283
Process Description .................. 283 Process Discussion ................... 291 Cost Estimates. .................... 292
APPENDIX A
DESIGN AND COST BASIS . . . . . . . . . . . . . . . . .
APPENDIX B
PHYSICAL PROPERTIES OF RAW MATERIALS . . . . . . . . . .
APPENDIX C
ION EXCHANGE RESIN CROSS REFERENCE CHART . . . . . . . .
CITED REFERENCES . . . . . . . . . . . . . . . . . . . . . . . 305
PATENT REFERENCESBYCOMPANY . . . . . . . . . . . . . . . . . 341
297
301
303
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ILLUSTRATIONS
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6.1 Manufacture of Poly(Styrene-DVB) Beads Flow Diagram . . . . . . . . . . . . . . . . . . . . . .
6.2 Manufacture of Poly(Styrene-DVB) Beads, Macroporous-Type Effect of Plant Capacity on Total Fixed Capital . . . .
6.3 Manufacture of Poly(Styrene-DVB) Beads Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . .
7.1 Sulfonation of Poly(Styrene-DVB) Beads for Strong-Acid Cation Exchangers Flow Diagram . . . . . . . . . . . . . . . . . . . . . .
7.2 Manufacture of Poly(Styrene-DVB) Strong-Acid Cation Exchange Resins
Effect of Plant Capacity on Total Fixed Capital . . . .
7.3 Sulfonation of Poly(Styrene-DVB) Beads for Strong-Acid Cation Exchangers Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . .
8.1 Chloromethylation of Poly(Styrene-DVB) Beads for Anion Exchangers Flow Diagram . . . . . . . . . . . . . . . . . . . . . .
9.1 Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers
Flow Diagram . . . . . . . . . . . . . . . . . . . . . .
9.2 Manufacture of Poly(Styrene-DVB) Anion Exchange Besins
Effect of Plant Capacity on Total Fixed Capital . . . .
9.3 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base, Type 1
Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . .
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357
190
194
359
213
216
361
363
244
246
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ILLUSTRATIONS
9.4 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base, Type 2
Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . , . . . . . . . . . 247
9.5 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base
Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . .
10.1 Manufacture of Poly(Methy1 Acrylate-DVB) Beads Flow Diagram . . . . . . . . . . . . . . . . . . . . . .
10.2 Manufacture of Poly(Methy1 Acrylate-DVB) Beads Effect of Plant Capacity on Total Fixed Capital . . . .
10.3 Manufacture of Poly(Methy1 Acrylate-DVB) Beads Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . .
11.1 Weak-Acid Acrylic Ion Exchangers by Hydrolysis of Poly(Methy1 Acrylate-DVB) Beads Flow Diagram . . . . . . . . . . . . . . . . . . . . . .
11.2 Weak-Acid Acrylic Ion Exchangers by Hydrolysis of Poly(Methy1 Acrylate-DVB) Beads
Effect of Plant Capacity on Total Fixed Capital . . . .
11.3 Weak-Acid Acrylic Ion Exchangers by Hydrolysis of Poly(Methy1 Acrylate-DVB) Beads Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . .
12.1 Weak-Base Acrylic Ion Exchangers by Aminolysis of Poly(Methy1 Acrylate-DVB) Beads Flow Diagram . . . . . . . . . . . . . . . . . . . . . .
248
365
265
268
367
280
282
369
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1.1 Classification of Ion Exchange Resins. . . . . . . . . .
2.1 Processes Evaluated. . . . . . . . . . . . . . . . . . .
2.2 Summary of Production Costs and Selling Prices for Ion Exchange Resins . . . . . . . . . . . . . . . . . .
2.3 Operating Premises for Poly(Styrene-DVB) Resin Plant . .
2.4 Capital Investment for Plant to Make 800,000 ft3/yr of Poly(Styrene-DVB) Ion Exchange Resins . . . . . . . . .
2.5 Capital Investment for Plant to Make 40,000 ft3/yr of Poly(Acrylate-DVB) Ion Exchange Resins. . . . . . . . .
3.1 Estimates of World Production Rates of Ion Exchange Resins . . . . . . . . . . . . . . . . . .
3.2 Rinds of Polymers Used for Ion Exchange Resins . . . . .
3.3 Percentage of Functional Types of Ion Exchange Resins Relative Amounts Produced. . . . . . . . . . . . . . . .
3.4 Estimates of Total Ion Exchange Resin Sales, 1976 . . .
3.5 U.S. Consumption Pattern for Ion Exchange Resins . . . .
3.6 West European Consumption Pattern for Ion Exchange Resins . . . . . . . . . . . . . . . . . .
3.7 U.S. Manufacturers of Ion Exchange Resins . . . . . . .
3.8 West European Manufacturers of Ion Exchange Resins . . .
3.9 East European Manufacturers of Ion Exchange Resins . . .
3.10 Japanese Imports of Ion Exchange Resins . . . . . . . .
5.1 Ion Exchangers--Anionic and Cationic Summary of General Patents . . . . . . . . . . . . . . .
5.2 Strong-Acid Cation Exchangers--Polystyrene Matrix Patent Summary.....................
5.3 Strong-Acid Cation Exchangers- Phenol-Formaldehyde Matrix Patentsunnnary.....................
5.4 Strong-Acid Cation Exchangers--Miscellaneous Matrices Patents~ry.................. . . .
5.5 Weak-Acid Cation Exchangers--Polystyrene Matrix Patentsunrmary................ . . . . .
3
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9
10
13
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16
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20
21
25
26
27
27
57
67
80
83
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5.6 Weak-Acid Cation Exchangers--Phenolic Matrix Patentsummary...... . . . . . . . . . . . . . . .
5.7 Weak-Acid Cation Exchangers--Acrylic Matrix Patentsumrmary................... . .
92
94
5.8 Weak-Acid Cation Exchangers--Miscellaneous Matrices Patentsummary...... . . . . . . . . . . . . . . .
5.9 Strong-Base Anion Exchangers--Polystyrene Matrix Patentsummnary.....................
100
107
5.10 Strong-Base Anion Exchangers--Miscellaneous Matrices PatentSummary...... . . . . . . . . . . . . . . .
5.11 Weak-Base Anion Exchangers--Polystyrene Matrix Patentsummary................. . . . .
5.12 Weak-Base Anion Exchangers--Acrylic Matrix PatentSummary...... . . . . . . . . . . . . . . .
5.13 Weak-Base Epoxy-Amine Anion Exchangers PatentSummary.... . . . . . . . . . . . . . . i..
5.14 Weak-Base Anion Exchangers--Miscellaneous Matrices Patent Summary.....................
5.15 Chloromethylation Patentsummary...... . . . . . . . . . . . . . . .
5.16 Chelating Ion Exchangers PatentSummary.... . . . . . . . . . . . . . . . . .
5.17 Amphoteric Ion Exchangers Patentsummary...... . . . . . . . . . . . . . . .
5.18 Hybrid or Composite Ion Exchangers Patentsrmmnary................. . . . .
6.1 Production Bate Assumptions for Poly(Styrene-DVB) Ion Exchangers . . . . . . . . . . .
6.2 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (4% or 8% DVB)
Design Bases and Assumptions . . . . . . . . . . . . . .
6.3 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type Major Equipment and Utilities Summary . . . . . . . . .
6.4 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (4% DVB)
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151
162
167
172
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StreamFlows . . . . . . . . . . . . . . . 6 . . . . . . 177
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6.5 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (8% DVB) Stream Flows . . . . . . . . . . . . . . . . . . . . . .
6.6 Manufacture of Poly(Styrene-DVB) Beads, Macroporous-Type Design Bases and Assumption. . . . . . . . . . . . . . .
6.7 Manufacture of Poly(Styrene-DVB) Beads, Macroporous-Type Major Equipment and Utilities Summary. . . . . . . . . .
6.8 Manufacture of Poly(Styrene-DVB) Beads, Macroporous-Type (16% DVB) StreamFlows. . . . . . . . . . . . . . . . . . . . . .
6.9 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type Total Capital Investment . . . . . . . . . . . . . . . .
6.10 Manufacture of Poly(Styrene-DVB) Beads, Macroporous-Type Total Capital Investment . . . . . . . . . . . . . . . .
6.11 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (4% DVB) Production Costs . . . . . . . . . . . . . . . . . . . .
6.12 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (8% DVB) Production Costs . . . . . . . . . . . . . . . . . . . .
6.13 Manufacture of Poly(Styrene-DVB) Beads, Macroporous-Type (16% DVB) Production Costs . . . . . . . . . . . . . . . . . . . .
7.1 Sulfonation of Poly(Styrene-DVB) Beads for Strong-Acid Cation Exchangers
Design Bases and Assumptions . . . . . . . . . . . . . .
7.2 Sulfonation of Poly(Styrene-DVB) Beads, Gel-Type, for Strong-Acid Cation Exchangers Major Equipment and Utilities. . . . . . . . . . . . . .
7.3 Sulfonation of Poly(Styrene-DVB) Beads, Gel-Type (8% DVB) for Strong-Acid Cation Exchangers . .
7.4 Sulfonation of Poly(Styrene-DVB) Beads, Macroporous-Type (16% DVB) for Strong-Acid Cation Exchangers Stream Flows . . . . . . . . . . . . . . . . . . . . . .
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7.5
7.6
7.7
7.8
7.9
8.1
8.2
8.3
8.4
9.1
9.2
9.3
Sulfonation of Poly(Styrene-DVB) Beads for Strong-Acid Cation Exchangers Summary of Waste Products. . . . . . . . . . . . . . . .
Sulfonation of Poly(Styrene-DVB) Beads, Gel-Type, for Strong-Acid Cation Exchangers Total Capital Investment . . . . . . . . . . . . . . . .
Sulfonation of Poly(Styrene-DVB) Beads, Macroporous-Type, for Strong-Acid Cation Exchangers Total Capital Investment . . . . . . . . . . . . . . . .
Sulfonation of Poly(Styrene-DVB) Beads, Gel-Type (8% DVB) for Strong-Acid Cation Exchangers Production Costs . . . . . . . . . . . . . . . . . . . .
Sulfonation of Poly(Styrene-DVB) Beads, Macroporous-Type (16% DVB) for Strong-Acid Cation Exchangers Production Costs . . . . . . . . . . . . . . . . . . . .
Chloromethylation of Poly(Styrene-DVB) Beads Design Bases and Assumptions . . . . . . . . . . . . . .
Chloromethylation of Poly(Styrene-DVB) Beads, Gel-Type (4% DVB) for Anion Exchangers StreamFlows . . . . . . . . . . . . . . . . . . . . . .
Chloromethylation of Poly(Styrene-DVB) Beads, Macroporous-Type (16% DVB), for Anion Exchangers StreamFlows . . . . . . . . . . . . . . . . . . . . . .
Chloromethylation of Poly(Styrene-DVB) Beads, Macroporous-Type for Anion Exchangers Summary of Waste Products. . . . . . . . . . . . . . . .
Lamination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers Design Bases and Assumptions . . . . . . . . . . . . . .
Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers
Major Equipment and Utilities Summary . . . . . . . . .
Amination of Chloromethylated Poly(Styrene-DVB) Beads -for Anion Exchangers, Strong-Base (Type l), Gel-Type Stream Flows . . . . . . . . . . . . . . . . . . . . . .
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211
212
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215
219
222
223
224
230
233
235
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9.4 Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type l), Macroporous-Type Stream Flows . . . . . . . . . . . . . . . . . . . . . . 236
9.5 Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type Z), Gel-Type Stream Flows. . . . . . . . . . . . . . . . . . . . . . 237
9.6 Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type 2), Macroporous-Type Stream Flows . . . . . . . . . . . . . . . . . . . . . . 238
9.7 Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, Gel-Type Stream Flows . . . . . . . . . . . . . . . . . . . . . . 239
9.8 Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, Macroporous-Type StreamFlows. . . . . . . . . . . . . . . . . . . . . . 240
9.9 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers Total Capital Investment . . . . . . . . . . . . . . . .
9.10 Manufacture of Poly(Styrene-DVB) Anion Exchange Resins Summary of Production Costs. . . . . . . . . . . . . . .
243
245
9.11 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type l), Gel-Type Production Costs . . . . . . . . . . . . . . . . . . . . 249
9.12 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type l), Macroporous-Type Production Costs . . . . . . . . . . . . . . . . . . . . 250
9.13 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type 2), Gel-Type Production Costs . . . . . . . . . . . . . . . . . . . . 251
9.14 Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type 2), Macroporous-Type Production Costs . . . . . . . . . . . . . . . . . . . . 252
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TABLES
9.15
9.16
10.1
10.2
10.3
10.4
10.5
10.6
11.1 .
11.2
11.3
11.4
Al.5
11.6
Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, Gel-Type
Production Costs . . . . . . . . . . . . . . . . . . . . 253
Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, Macroporous-Type Production Costs . . . . . . . . . . . . . . . . . . . . 254
MANUFACTURE OF POLY(METRYL ACRYLATE-DVB) BEADS
Design Bases and Assumptions . . . . . . . . . . . . . .
Major Equipment and Utilities Summary . . . . . . . . .
Manufacture of Poly(Methy1 Acrylate-DVB) Beads, Gel-Type
256
259
Stream Flows . . . . . . . . . . . . . . . . . . . . . . 261
Manufacture of Poly(Methy1 Acrylate-DVB) Beads, Macroporous-Type StreamFlows . . . . . . . . . . . . . . . . . . . . . . 262
MANUFACTURE OF POLY(METHYL ACRYLATE-DVB) BEADS
Total Capital Investment . . . . . . . . . . . . . . . .
Production Costs . . . . . . . . . . . . . . . . . . . .
WEAK-ACID ACRYLIC ION EXCRANGERS BY HYDROLYSIS OF POLY(METEIYL ACRYLATE-DVB) BEADS
Design Bases and Assumptions . . . . . . . . . . . . . .
Major Equipment and Utilities Summary . . . . . . . . .
StreamFlows. . . . . . . . . . . . . . . . . . . . . .
Summary of Waste Streams . . . . . . . . . . . . . . . .
WEAK-ACID ACRYLIC ION EXCHANGERS BY HYDROLYSIS OF POLY(METRYL ACRYLATE-DVB) BEADS, MACROPOROUS-TYPE
Total Capital Investment . . . . . . . . . . . . . . . .
Production Costs . . . . . . . . . . . . . . . . . . . .
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270
273
275
276
279
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TABLES
WEAK-BASE *ACRYLIC ION EXCHANGERS BY AMINOLYSIS OF POLY(METRYL ACRYLATE-DVB) BEADS
12.1 Design Bases and Assumptions . . . . . . . . . . . . . 284
12.2 Major Equipment and Utilities Summary. . . . . . . . . . 287
12.3 Stream Flows . . . . . . . . . . . . . . . . . . . . . . 289
12.4 Summary of Waste Streams . . . . . . . . . . . . . . . . 290
WEAR-BASE ACRYLIC ION EXCHANGERS BY AMINOLYSIS OF POLY(METRYL ACRYLATE-DVB) BEADS, MACROPOROUS-TYPE
12.5 Total Capital Investment . . . . . . . . . . . . . . . . 294
12.6 Production Costs . . . . . . . . . . . . . . . . . . . . 295
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