PROCESS ECONOMICS PROGRAM
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1 PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California Process Economics Program Report No. 61C CHLORINR (December 1982) Abstract In this report SRI comprehensively reviews the technology of salt electrolysis to make chlorine and sodium hydroxide. l'he economics of the three processes--the diaphragm, the mercury, and the membrane--are compared under various conditions and at different capacities. We evaluate the synthesis of soda ash by the classic Solvay process and two modified versions of it (one that by-produces ammonium chloride and another that uses trimethylamine). Processes for recovery of natural soda ash from trona are reviewed; the monohydrate process and a process using solution-mined trona are evaluated. In view of the ever-increasing cost of caustic soda relative to the cost of natural soda ash, caustieation of soda ash as an integral part of making soda ash from trona is studied, and two processes are evaluated: one using solid-mined trona, and one using solution-mined trona. Processes for making caustic soda without coproducing chlorine are reviewed. PEP'82 YCY
2 Report No. 61C CHLORINE SUPPLEMENT C by YEN-CHEN YEN with contributions by CHIEN NIEH a L cl 1 m December 1982 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 chemicals and 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 DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe. ii
4 CONTENTS 1 INTRODUCTION 1 2 SUMMARY..,... General Aspects.. Technical Aspects. Membrane Process for Salt Solution Electrolysis. Ammonia Soda Process (Solvay Process) for Making Sodium Carbonate Trimethylamine Process for Making go&n'c;rbo~a;e' Recovery of Sodium Carbonate from Solid Trona... Recovery of Sodium Carbonate from Solution Mined Trona.. Caustization of Sodium Carbonate Solution from Trona INDUSTRY STATUS Chlorine and Caustic Soda SodaAsh REVIEW OF PROCESSES FOR SALT ELECTROLYSIS... Brine... Anodes... Cathodes... Diaphragms... Diaphragm Cells... Sodium Hydroxide Concentration... Sodium Hydroxide Purification... Mercury Cells... Membranes... Chemical Composition of Membranes... Manufacture of Membranes... Commercial Grades... An IdealMembrane... Membrane Cells... Solid Polymer Electrode Cells... Comparison of Processes... Hybrid Process and Combination of Processes... Electrolysis of Molten Salt in a Cell with a CeramicMembrane.... Chlorine... Hydrogen... Electrical Features iii
5 5 CHLORINE-ALKALI BY ELECTROLYSIS... Diaphragm Process... Mercury Process... Membrane Process... Process Description... Process Discussion... Cost Estimates... Comparison of the Three Processes , SODIUM CARBONATE BY CONVENTIONAL AMMONIA SODA PROCESS 163 Chemistry Review of Process Process Description Process Discussion Cost Estimates SODIUM CARBONATE BY MODIFIED AMMONIA SODA PROCESSES. Sodium Carbonate with Coproduction of Ammonium Chloride (an update) Sodium Carbonate by Trimethylamine Process. 8 SODIUM CARBONATE FROM TRONA Review of Processes Sodium Carbonate from T&n: ~y'm;moh;d;a;e'p;ocess'. 226 Process Description.., Process Discussion 233 Cost Estimates Sodium Carbonate f;k ;rg by'skxo;l l&~g* Process Description 239 Process Discussion 245 Cost Estimate....* CAUSTIZATION OF SODA ASH.... Sodium Hydroxide from a Carbonate Solution from Solution Mined Trona... Process Description... Process Discussion... CostEstimates... Sodium Hydroxide from a Carbonate Solution from SolidTrona IV
6 CONTENTS 10 OTRERPROCESSES Processes for Making Chlorine Without Alkali Coproduction. 271 Processes for Making Sodium Carbonate by Electrolysis from Sodium Hydroxide 271 Other Processes for Making Sodium Carbonate. 274 Other Processes for Making Sodium Hydroxide. 274 Suggestions for Improving the Process for Making Caustic Soda by Electrolysis of Sodium Sulfate APPENDIXA DESIGN AND COST BASES APPENDIXB AMMONIUM CBLORIDE AS A FERTILIZER. 283 CITEDREPERENCES. 285 PATENT REFERENCES BY COMPANY V
7 a Sodium Hydroxide and Chlorine by Membrane Process Plowsheet Sodium Hydroxide and Chlorine by Electrolysis Capital Investment Comparison Sodium Hydroxide and Chlorine by Electrolysis Product Value Comparison. 161 Sodium Hydroxide and Chlorine by Electrolysis Energy Requirement Comparison Flowsheet Sodium Carbonate by TMA Process Flowsheet...,. 369 Sodium Carbonate from Trona by Monohydrate Process Flowsheet Sodium Carbonate from Trona by Solution Mining Flowsheet Sodium Hydroxide from Trona by Solution Mining PlowSheet Sodium Hydroxide from Soda Solution from Solid Trona A Suggested Device for Making Sodium Hydroxide by Electrolysis of Sodium Sulfate,278 Vii
8 TABLES Sodium Hydroxide and Chlorine by Electrolyses of Sodium Chloride Solution Summary of Economics Sodium Carbonate Production Summary of Economics Caustization of Sodium Carbonate from Trona Summary of Economics Chlorine and Sodium Hydroxide Producers in the United States Chlorine and Sodium Hydroxide Producers in Western Europe Chlorine and Sodium Hydroxide Producers in Japan ' Chlorine and Sodium Hydroxide Producers in Canada, OPEC, and Australia Plants Using Membrane Processes in the World Chlorine and Sodium Hydroxide Production in the United States Chlorine Consumption in the United States Sodium Hydroxide Consumption in the United States List Prices of Chlorine and Sodium Hydroxide in the United States Sodium Carbonate Producers in the United States Sodium Carbonate Producers in Western Europe Sodium Carbonate Producers in Japan Sodium Carbonate Producers in Other Countries List Price of Sodium Carbonate in the United States Treatment of Feed Brine and Weak Brine PatentSummary Anodes PatentSummary Cathodes Patent Summary ix
9 TABLES 4.4 Oxygen Electrodes as Cathodes (Depolarized Cathodes) Patent Summary Diaphragms (permeable Separators) PatentSummary Diaphragm Cell Construction PatentSummary Diaphragm Cell Operation PatentSummary Bipolar Electrodes and Bipolar Cells PatentSumary Caustic Soda Concentration PatentSummary Caustic Soda Purification PatentSummary Mercury Process PatentSummary Mercury Recovery in Mercury Process PatentSummary Membranes Used in Salt Electrolysis PatentSummary Comparison of Membrane Compositions Membrane Cell Construction PatentSummary Membrane Cell Operation PatentSummary Membrane Cells Comparison of Monopolar and Bipolar Construction Membrane Cells Made by Asahi Chemical, Eltech and ICI Operating Characteristics of Asahi Chemical Cell Operating Characteristics of PM 21 Cell Operating Characteristics of Eltech MCC Cell X
10 TABLES Chlorine Recovery PatentSunnnary Hydrogen Recovery Patent Summary Electrical Features PatentSummary Sodium Hydroxide and Chlorine by Diaphragm Process Design Bases and Assumptions 5.2 Sodium Hydroxide and Chlorine by Diaphragm Process Total Capital Investment Other Features Relating to Membrane Process PatentSummary... Technical Characteristics of De Nora SPE Cells... Cells with Membrane in Contact with at Least One Electrode, and Solid Polymer Electrolyte (SPE) Cells PatentSummary... Operating Differences Among Diaphragm, Mercury, and Membrane Processes... Quality of Products Made by Diaphragm, Mercury, and Membrane Processes... Comparative Ratings of Diaphragm, Mercury, and Membrane Processes... Ceramic Membranes PatentSuvanary... Sodium Hydroxide and Chlorine by Diaphragm Process Capital Investment by Section... Sodium Hydroxide and Chlorine by Diaphragm Process Production Costs.. Cost Effects of Sodium Hydroxide and Chlorine by Diaphragm Process Starting f.rom Solid Salt Instead of from Brine... Sodium Hydroxide and Chlorine by Mercury Process Design Bases and Assumptions Xi
11 TABLES Sodium Hydroxide and Chlorine by Mercury Process Total Capital Investment. Sodium Hydroxide and Chlorine by Mercury Process Capital Investment by Section.. Sodium Hydroxide and Chlorine by Mercury Process Production Costs. Cost Effects of Sodium Hydroxide and Chlorine by Mercury Process Starting from Solid Salt Instead of from Brine.. Sodium Hydroxide and Chlorine by Membrane Process Design Bases and Assumptions... Sodium Hydroxide and Chlorine by Membrane Process StreamFlows... Sodium Hydroxide and Chlorine by Membrane Process Major Equipment. Sodium Hydroxide and Chlorine by Membrane Process Utilities Summary Sodium Hydroxide and Chlorine by Membrane Process Total Capital Investment. Sodium Hydroxide and Chlorine by Membrane Process Production Costs. Membrane Process Cost Effects of Design Variations PatentSummary... Design Bases and Assumptions... StreamFlows... Major Equipment. Utilities Summary Xii
12 TABLES Total Capital Investment. Capital Investment by Section.. Production Costs. Modified Anunonia Soda Process PatentSummary... Processes Using Amines in Producing Sodium Carbonate PatentSummary... Cost Comparison Between the Conventional Ammonia Soda Process and the Process with By-Production of AmmoniumChloride... Sodium Carbonate by TMA Process StreamFlows... Sodium Carbonate by TMA Process Total Capital Investment. Sodium Carbonate by TMA Process Production Costs. Sodium Carbonate from Trona by the Sesquicarbonate Process or Similar Processes PatentSummary... Sodium Carbonate from Trona by the Monohydrate Process and Related Processes PatentSuannary... Other Processes Related to Sodium Carbonate from Trona PatentSummary... Solution Mining of Trona PatentSummary... Sodium Carbonate from Trona Containing Fluoride PatentSummary... Sodium Carbonate from a Carbonate-Containing Brine PatentSummary... Sodium Carbonate from Trona by Monohydrate Process Design Bases and Assumptions Xiii
13 TABLES 8.8 a Sodium Carbonate from Trona by Monohydrate Process StreamFlows Sodium Carbonate from Trona by Monohydrate Process Major Equipment. 230 Sodium Carbonate from Trona by Monohydrate Process Utilities Summary 232 Sodium Carbonate from Trona by Monohydrate Process Total Capital Investment. 235 Sodium Carbonate from Trona by Monohydrate Process Production Costs. 237 Sodium Carbonate from Trona by Solution Mining Design gases and Assumptions Sodium Carbonate from Trona by Solution Mining StreamFlows Sodium Carbonate from Trona Solution by Mining Major Equipment. 243 Sodium Carbonate from Trona Solution by Mining Utilities Summary 244 Sodium Carbonate from Trona Solution by Mining Total Capital Investment Sodium Carbonate from Trona Solution by Mining Production Costs Sodium Hydroxide from Trona by Solution Mining Design Bases and Assumptions Sodium Hydroxide from TroM by Solution Mining StreamFlows...~ Sodium Hydroxide from Trona by Solution Mining Major Equipment Sodium Hydroxide from Trona by Solution Mining Utilities Summary Sodium Hydroxide from Trona by Solution Mining Total Capital Investment Sodium Uydroxide from Trona by Solution Mining Production Costs. 260 xiv
14 i TABLES Sodium Hydroxide from Trona by Solution Mining Usages for Sodium Hydroxide Alone. Sodium Hydroxide from Soda Solution from Solid TroM StreamFlows. Sodium Hydroxide Soda Solution Solid Trona Capital Investment. Sodium from Soda from Solid Production Costs Hydroxide from Solution from TrOM Usages Sodium Hydroxide... Comparison Product Values Sodium Hydroxide by Different. Chlorine Sodium Hydrochloric Acid. from Wastes. Summary Sodium by Other PatentSummary xv
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