WET PROCESS PHOSPHORIC ACID

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1 Report No. 8B WET PROCESS PHOSPHORIC ACID Supplement B by GEORGE E. HADDELAND December 1974 A private report by the PROCESS ECONOMICS PROGRAM * STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA

2 CONTENTS 1 INTRODUCTION SUMMARY Production, Raw Material, and Prices... Phosphoric Acid Processes... ;... Technology... Economics... Other Phosphoric Acid Processes... Purified Phosphoric Acids... Technology... Economics... Acid Concentration By-Product Recovery... INDUSTRY STATUS Phosphoric Acid Production... Phosphoric Acid Price... Raw Material Costs CHEMISTRY Sulfuric Acid Decomposition of Phosphate Rock Hemihydrate-Dihydrate Transformation Rates PHOSPHORIC ACID BY THE DIHYDRATE PROCESS Recent Developments General Two-Stage Phosphoric Acid Reactors Dihydrate Process Patents Process Control Process Description Process Discussion Cost Estimates Capital Investment Production Costs Discussion of Costs Conclusions PHOSPHORIC ACID BY THE HEMIHYDRATE-DIHYDRATE PROCESS Introduction Hemihydrate-Dihydrate Process Variations Hemihydrate-Dihydrate Process Patents vii

3 CONTENTS 6 (Continued) Process Description Process Discussion Cost Estimates Capital Investment Production Costs Discussion of Costs Conclusions PHOSPHORIC ACID BY THE HEMIHYDRATE PROCESS Introduction Hemihydrate Process Developments New Patents 112 New Process Information Process Description Process Discussion Cost Estimates Capital Investment Production Costs Cost Comparison of Dihydrate, Hemihydrate-Dihydrate, and Hemihydrate Processes OTHER PHOSPHORIC ACID PROCESSES Recycle Sulfuric Acid Recycle Ammonium Bisulfate Process Nitric Acid Acidulation of Phosphate Rock Anhydrite Processes PURIFICATION OF WET PROCESS PHOSPHORIC ACID Introduction Purification Technology Recent Solvent Extraction Patents Chemical and Physical Purification Patents Solvent Purification Processes Type I: Solvent Extraction of Wet Process Phosphoric Acid Process Description Process Discussion Cost Estimates Capital Cost Production Costs Discussion of Costs Conclusion viii

4 CONTENTS 9 (Continued) Type II: Solvent Extraction of Superphosphate Solids Process Description Process Discussion Cost Estimates Capital Cost Production Costs Discussion of Costs Conclusions WET PROCESS ACID CONCENTRATION Introduction Orthophosphoric Acid Solids Precipitation Fluorine Removal Other Concentration Methods Capital and Production Costs Superphosphoric Acid Vacuum Concentration Hot Gas and Submerged Combustion Concentration Acid Entrainment Process Description Process Discussion Cost Estimates Capital Investment... I Production Costs Discussion of Costs BY-PRODUCT RECOVERY... Introduction... Uranium and Vanadium Oxides... By-Product Gypsum... By-Product Fluorine... Recovery... Use of Fluosilicic Acid... Fluosilicic Acid Recovery... Process Description... Process Discussion... Cost Estimates... Capital Investment... Production Costs... Discussion of Costs... Conclusions ix

5 CONTENTS APPENDIX A DESIGN AND COST BASIS APPENDIX B PHYSICAL DATA APPENDIX C ANALYSIS AND SPECIFICATIONS APPENDIX D CORROSION, WASTE DISPOSAL, AND POLLUTION CONTROL CITED REFERENCES PATENT REFERENCES BY COMPANY X

6 ILLUSTRATIONS Production of Phosphoric Acid or Phosphate Fertilizers in United States, Japan, and Europe Phosphoric Acid Price History Stability of Calcium Sulfate Hydrates with Varying Temperature and Acid Concentrations Calcium Sulfate Hemihydrate to Dihydrate Effect of Sulfuric Acid Concentration on the Hydration Time Swenson Two-Stage Phosphoric Acid Reactor The Kellogg-Lopker Attack System Estimated Capital Investment as a Function of Plant Capacity Estimated Production Cost of Phosphoric Acid by the Dihydrate Process as a Function of Plant Size, Operating Rate, and Raw Materials Costs Variations of Semihydrate-Dihydrate Phosphoric Acid Processes Phosphoric Acid by the Hemihydrate-Dihydrate Process Phosphoric Acid by the Hemihydrate-Dihydrate Process Estimated Capital Investment as a Function of Plant Capacity Phosphoric Acid Production Cost by the Hemihydrate-Dihydrate Process as a Function of Plant Design Capacity and Operating Level Phosphoric Acid by the Hemihydrate Process Comparative Production Costs and Battery Limits Investments for Dihydrate, Hemihydrate, and Hemihydrate-Dihydrate Phosphoric Acid (54% PaOs) Plants RABS Phosphoric Acid Process Processes to Purify or Upgrade Wet Process Phosphoric Acid Solvent Purification of Wet Process Phosphoric Acid xi

7 ILLUSTRATIONS B.l Estimated Battery Limits, Fixed Capital Investments, and Operating Cost for Upgrading Wet Process Phosphoric Acid to Technical Grade Material Phosphoric Acid by Solvent Extraction of Superphosphate Comparison of Investment and Production Costs for Technical Phosphoric Acid by Solvent Extraction of Superphosphate and Phosphoric Acid at Various Plant Capacities Battery Limits and Utilities Investment for Concentration to Orthophosphoric Acid (54% P,O,) Wet Process Phosphoric Acid Concentration Cost as a Function of Feed Acid Concentration, Plant Design, Capacity, and Steam Cost Concentration of Orthophosphoric Acid to Superphosphoric Acid Concentration of Orthophosphoric Acid to Superphosphoric Acid Variation of Capital Investment and Production Cost with Plant Capacity Possible Uses for By-Product Phosphogypsum Phosphoric Acid Plant Sources of Fluorine and Its Potential Products By-Product Fluosilicic Acid from Wet Process Phosphoric Acid plants Estimated Fixed Capital Investment and Net Production Cost as a Function of Fluosilicic Acid Absorption Capacity Phase Diagram: Water-Diisopropyl Ether-Phosphoric Acid xii

8 TABLES Summary of Economics for Dihydrate, Hemihydrate, and Hemihydrate-Dihydrate Phosphoric Acid Processes Comparitive Economics to Upgrade Phosphoric Acid to Technical Quality by Solvent Extractions of Wet Process Phosphoric Acid or Superphosphate Producers of Wet Process Phosphoric Acid in the United States Major Wet Process Phosphoric Acid Producers Outside the United States List Prices for Florida Phosphate Rock Supplied to Export Markets..., List Prices for Moroccan Phosphate Rock Supplied to Export Markets Patent Summary Major Process Equipment and Utilities Summary Stream Flows Total Capital Investment Production Costs A Comparison of Various Hemihydrate-Dihydrate Processes Phosphoric Acid by Hemihydrate-Dihydrate Processes Patent Summary Phosphoric Acid by the Hemihydrate-Dihydrate Process Major Process Equipment and Utilities Summary Phosphoric Acid by the Hemihydrate-Dihydrate Process Stream Flows Phosphoric Acid by the Hemihydrate-Dihydrate Process Total Capital Investment Phosphoric Acid by the Hemihydrate-Dihydrate Process Production Costs xiii

9 TABLES Phosphoric Acid by Hemihydrate Processes Patent Summary Phosphoric Acid by the Hemihydrate Process Major Process Equipment and Utilities Summary Phosphoric Acid by the Hemihydrate Process Stream Flows Phosphoric Acid by the Hemihydrate Process Total Capital Investment Phosphoric Acid by the Hemihydrate Process Production Costs Comparative Phosphoric Acid Process Economics Purification of Wet Process Acid by Solvent Extraction Patent Summary Purification of Wet Process Acid by Chemical and Physical Methods Patent Summary Solvent Purification of Wet Process Phosphoric Acid Major Process Equipment and Utilities Summary Solvent Purification of Wet Process Phosphoric Acid Stream Flows Solvent Purification of Wet Process Phosphoric Acid Total Capital Investment Solvent Purification of Wet Process Phosphoric Acid Production Costs Furnace Phosphoric Acid Summary of Estimated Investment and Production Costs Phosphoric Acid by Solvent Extraction of Superphosphate Major Process Equipment and Utilities Summary Phosphoric Acid by Solvent Extraction of Superphosphate Stream Flows Phosphoric Acid by Solvent Extraction of Superphosphate Total Capital Investment Phosphoric Acid by Solvent Extraction of Superphosphate Production Costs xiv

10 TABLES Economics of Orthophosphoric Acid Concentration Concentration to Superphosphoric Acid Major Process Equipment and Utilities Summary Concentration to Superphosphoric Acid Stream Flows Concentration to Superphosphoric Acid Total Capital Investment Concentration to Superphosphoric Acid Production Costs Phosphogypsum Purification Patent Summary Fluorine Removal and Concentration from Wet Process Phosphoric Acid Off-Gases Patent Summary Fluorine Removal from Wet Process Phosphoric Acid Patent Summary Processes Using Fluosilicic Acid as a Raw Material Patent Summary By-Product Fluosilicic Acid from Wet Process Phosphoric Acid Plants Major Process Equipment and Utilities Summary....., By-Product Fluosilicic Acid from Wet Process Phosphoric Acid Plants Stream Flows By-Product Fluosilicic Acid from Wet Process Phosphoric Acid Plants Total Capital Investment By-Product Fluosilicic Acid from Wet Process Phosphoric Acid Plants Production Costs xv

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