Ad+=--= Abstract. Process Economics Program Report No. 124 ION EXCHANGE RESINS. (December 1979)

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1 Ad+=--= &-==+ --AA. PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California Abstract Process Economics Program Report No. 124 ION EXCHANGE RESINS (December 1979) Ion exchange resins are produced in most major industrial countries 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

2 Report No. 124 ION EXCHANGE RESINS by GRANT E. RUSSELL December 1979 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

3 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, product, and plant for the United States and Western Europe.

4 CONTENTS 1 INTRODUCTION SUMMARY INDUSTRY STATUS 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 REVIEW OF PROCESSES 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 MANUFACTURE OF POLY(STYRENE-DVB) STRONG-ACID CATION EXCHANGERS Process Descriptions... Process Discussion... Cost Estimates CHLOROMETHYLATION OF POLY(STYRENE-DVB) BEADS Process Description Process Discussion Cost Estimates AMINATION OF CHLOROMETHYLATED POLY(STYRENE-DVB) Process Description Cost Estimates ix

5 CONTENTS 10 MANUFACTURE OF POLY(METHYL ACRYLATE-DVB) BEADS Process Description Process Discussion CostEstimates MANUFACTURE OF WEAK-ACID ACRYLIC ION EXCHANGERS Process Discussion Cost Estimates MANUFACTURE OF WEAK-BASE ACRYLIC RESINS Process Description Process Discussion Cost Estimates APPENDIX A DESIGN AND COST BASIS APPENDIX B PHYSICAL PROPERTIES OF RAW MATERIALS APPENDIX C ION EXCHANGE RESIN CROSS REFERENCE CHART CITED REFERENCES PATENT REFERENCESBYCOMPANY X

6 ILLUSTRATIONS 6.1 Manufacture of Poly(Styrene-DVB) Beads Flow Diagram Manufacture of Poly(Styrene-DVB) Beads, Effect of Plant Capacity on Total Fixed Capital Manufacture of Poly(Styrene-DVB) Beads Effect of Operating Level and Plant Capacity on Production Cost Sulfonation of Poly(Styrene-DVB) Beads for Strong-Acid Cation Exchangers Flow Diagram Manufacture of Poly(Styrene-DVB) Strong-Acid Cation Exchange Resins Effect of Plant Capacity on Total Fixed Capital Sulfonation of Poly(Styrene-DVB) Beads for Strong-Acid Cation Exchangers Effect of Operating Level and Plant Capacity on Production Cost Chloromethylation of Poly(Styrene-DVB) Beads for Anion Exchangers Flow Diagram Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers Flow Diagram Manufacture of Poly(Styrene-DVB) Anion Exchange Besins Effect of Plant Capacity on Total Fixed Capital 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

7 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 , Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base Effect of Operating Level and Plant Capacity on Production Cost Manufacture of Poly(Methy1 Acrylate-DVB) Beads Flow Diagram Manufacture of Poly(Methy1 Acrylate-DVB) Beads Effect of Plant Capacity on Total Fixed Capital Manufacture of Poly(Methy1 Acrylate-DVB) Beads Effect of Operating Level and Plant Capacity on Production Cost Weak-Acid Acrylic Ion Exchangers by Hydrolysis of Poly(Methy1 Acrylate-DVB) Beads Flow Diagram Weak-Acid Acrylic Ion Exchangers by Hydrolysis of Poly(Methy1 Acrylate-DVB) Beads Effect of Plant Capacity on Total Fixed Capital Weak-Acid Acrylic Ion Exchangers by Hydrolysis of Poly(Methy1 Acrylate-DVB) Beads Effect of Operating Level and Plant Capacity on Production Cost Weak-Base Acrylic Ion Exchangers by Aminolysis of Poly(Methy1 Acrylate-DVB) Beads Flow Diagram Xii

8 1.1 Classification of Ion Exchange Resins Processes Evaluated Summary of Production Costs and Selling Prices for Ion Exchange Resins Operating Premises for Poly(Styrene-DVB) Resin Plant Capital Investment for Plant to Make 800,000 ft3/yr of Poly(Styrene-DVB) Ion Exchange Resins Capital Investment for Plant to Make 40,000 ft3/yr of Poly(Acrylate-DVB) Ion Exchange Resins Estimates of World Production Rates of Ion Exchange Resins Rinds of Polymers Used for Ion Exchange Resins Percentage of Functional Types of Ion Exchange Resins Relative Amounts Produced Estimates of Total Ion Exchange Resin Sales, U.S. Consumption Pattern for Ion Exchange Resins West European Consumption Pattern for Ion Exchange Resins U.S. Manufacturers of Ion Exchange Resins West European Manufacturers of Ion Exchange Resins East European Manufacturers of Ion Exchange Resins Japanese Imports of Ion Exchange Resins Ion Exchangers--Anionic and Cationic Summary of General Patents Strong-Acid Cation Exchangers--Polystyrene Matrix Patent Summary Strong-Acid Cation Exchangers- Phenol-Formaldehyde Matrix Patentsunnnary Strong-Acid Cation Exchangers--Miscellaneous Matrices Patents~ry Weak-Acid Cation Exchangers--Polystyrene Matrix Patentsunrmary Xiii

9 TABLES 5.6 Weak-Acid Cation Exchangers--Phenolic Matrix Patentsummary Weak-Acid Cation Exchangers--Acrylic Matrix Patentsumrmary Weak-Acid Cation Exchangers--Miscellaneous Matrices Patentsummary Strong-Base Anion Exchangers--Polystyrene Matrix Patentsummnary Strong-Base Anion Exchangers--Miscellaneous Matrices PatentSummary Weak-Base Anion Exchangers--Polystyrene Matrix Patentsummary Weak-Base Anion Exchangers--Acrylic Matrix PatentSummary Weak-Base Epoxy-Amine Anion Exchangers PatentSummary i Weak-Base Anion Exchangers--Miscellaneous Matrices Patent Summary Chloromethylation Patentsummary Chelating Ion Exchangers PatentSummary Amphoteric Ion Exchangers Patentsummary Hybrid or Composite Ion Exchangers Patentsrmmnary Production Bate Assumptions for Poly(Styrene-DVB) Ion Exchangers Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (4% or 8% DVB) Design Bases and Assumptions Manufacture of Poly(Styrene-DVB) Beads, Gel-Type Major Equipment and Utilities Summary Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (4% DVB) StreamFlows xiv

10 6.5 Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (8% DVB) Stream Flows Manufacture of Poly(Styrene-DVB) Beads, Design Bases and Assumption Manufacture of Poly(Styrene-DVB) Beads, Major Equipment and Utilities Summary Manufacture of Poly(Styrene-DVB) Beads, (16% DVB) StreamFlows Manufacture of Poly(Styrene-DVB) Beads, Gel-Type Total Capital Investment Manufacture of Poly(Styrene-DVB) Beads, Total Capital Investment Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (4% DVB) Production Costs Manufacture of Poly(Styrene-DVB) Beads, Gel-Type (8% DVB) Production Costs Manufacture of Poly(Styrene-DVB) Beads, (16% DVB) Production Costs Sulfonation of Poly(Styrene-DVB) Beads for Strong-Acid Cation Exchangers Design Bases and Assumptions Sulfonation of Poly(Styrene-DVB) Beads, Gel-Type, for Strong-Acid Cation Exchangers Major Equipment and Utilities Sulfonation of Poly(Styrene-DVB) Beads, Gel-Type (8% DVB) for Strong-Acid Cation Exchangers Sulfonation of Poly(Styrene-DVB) Beads, (16% DVB) for Strong-Acid Cation Exchangers Stream Flows xv

11 . TABLES 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,, 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, (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, (16% DVB), for Anion Exchangers StreamFlows Chloromethylation of Poly(Styrene-DVB) Beads, 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 xvi

12 TABLES 9.4 Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type l), Stream Flows Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type Z), Gel-Type Stream Flows Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type 2), Stream Flows Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, Gel-Type Stream Flows Amination of Chloromethylated Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, StreamFlows Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers Total Capital Investment Manufacture of Poly(Styrene-DVB) Anion Exchange Resins Summary of Production Costs Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type l), Gel-Type Production Costs Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type l), Production Costs Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type 2), Gel-Type Production Costs Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Strong-Base (Type 2), Production Costs xvii

13 TABLES Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, Gel-Type Production Costs Chloromethylation and Amination of Poly(Styrene-DVB) Beads for Anion Exchangers, Weak-Base, Production Costs 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 Stream Flows Manufacture of Poly(Methy1 Acrylate-DVB) Beads, StreamFlows MANUFACTURE OF POLY(METHYL ACRYLATE-DVB) BEADS 10.5 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 Al.5 Total Capital Investment Production Costs xviii

14 TABLES WEAK-BASE *ACRYLIC ION EXCHANGERS BY AMINOLYSIS OF POLY(METRYL ACRYLATE-DVB) BEADS 12.1 Design Bases and Assumptions Major Equipment and Utilities Summary Stream Flows Summary of Waste Streams WEAR-BASE ACRYLIC ION EXCHANGERS BY AMINOLYSIS OF POLY(METRYL ACRYLATE-DVB) BEADS, MACROPOROUS-TYPE 12.5 Total Capital Investment Production Costs xix

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