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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

Report No. 124

ION EXCHANGE RESINS

by GRANT E. RUSSELL

December 1979

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 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.

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

7

8

9

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

ix

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32 35 37 37 40 41 45 46 49 50

173

179 184 186

195

196 205 207

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

Xi

357

190

194

359

213

216

361

363

244

246

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

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9

10

13

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16

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25

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57

67

80

83

88

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TABLES

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)

116

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128

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136

146

151

162

167

172

174

176

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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200

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

204

211

212

214

215

219

222

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224

230

233

235

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TABLES

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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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267

270

273

275

276

279

281

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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