FURNACEPHOSPHORUS AND PHOSPHORICACID PROCESS ECONOMICS PROGRAM. Report No. 52. July A private report by. the

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1 Report No. 52 FURNACEPHOSPHORUS AND PHOSPHORICACID by GEORGE E. HADDELAND July 1969 A private report by. the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA

2 CONTENTS 1 INTRODUCTION SUMMARY..., 3 3 INDUSTRY STATUS Phosphorus Production Phosphorus Consumption Fertilizer Phosphoric Acid Phosphates in Detergents Phosphorus and Phosphoric Acid Price History Raw Material Prices Phosphorus Transportation CHEMISTRY... Historical... Elemental Phosphorus... White Phosphorus... Red Phosphorus... Black Phosphorus... Phosphorus Compounds... Phosphorus Pentoxide... Phosphorus Oxidation Mechanism... Sodium Phosphates... Phosphorus Production Chemistry... 5 ELECTRIC FURNACE PRODUCTION OF PHOSPHORUS... Introduction... Phosphorus Furnace Design... Rectangular Furnaces... Circular Furnaces... *... Feed Preparation Methods... Phosphate Agglomeration Methods... Feed Preparation and Furnace Patents... Phosphorus Condensation and Recovery... Process Description... Process Discussion... Cost Estimates... Capital Investment... Production Costs... Discussion of Costs iii

3 CONTENTS 6 PHOSPHORIC ACID FROM PHOSPHORUS Review of Technology Combustion Process Process Development... ; Materials of Construction Development of the Stainless Steel Acid Plant TVA Process Process Description Process Discussion Cost Estimates Capital Investment Production Costs Discussion of Costs Areas for Possible Cost Reduction Comparative Cost of Wet Process Acid FUEL FURNACE PRODUCTION OF PHOSPHORUS Introduction Blast Furnace Phosphorus Historical TVA Research Victor Chemical's Development Blast Furnace Economics Recent Furnace Research Plasma Arc and Nuclear Heat Sources Fluidized Bed Reactors The Kellogg Reduction System Externally Heated Reactors Rotary Kiln Reactors Process Description Process Discussion Heat Transfer and Refractory Selection Problems Alternative Furnace Design Heat Utilization Cost Estimates Capital Investment Production Costs Discussion of Costs iv

4 CONTENTS PHOSPHORIC ACID BY STEAM OXIDATION OF PHOSPHORUS Introduction TVA Research TVA Pilot Plant Trials Process Description Process Discussion Cost Estimates Capital Investment Production Costs Discussion of Costs OTHER PROCESSES Hydrogen Reduction of Aluminum Phosphate Coproduction of Phosphorus and Calcium Carbide UTILIZATION OF PHOSPHORUS FURNACE BY-PRODUCTS Calcium Silicate Slag Ferrophosphorus... ; Precipitator Dust Carbon Monoxide Gases Fluorine APPENDIX A DESIGN AND COST BASIS... APPENDIX B PHYSICAL DATA... APPENDIX C ANALYSES AND SPECIFICATIONS APPENDIX D MATERIALS OF CONSTRUCTION, SAFETY AND HANDLING, AND POLLUTIONS CITED REFERENCES... PATENT REFERENCES BY COMPANY

5 ILLUSTRATIONS Comparative Production Costs for 72% P2O5, Phosphoric Acid by Fuel Furnace and Wet Process Plants... U.S. and World Production of Phosphorus... Approximate Transportation Costs for One Ton of Phosphorus Pentoxide... Allotropes of Phosphorus... Rate of Phosphate Matrix Reduction When Heated with Carbon and silica... Equilibrium Temperature-Composition Diagram for the Liquid System CaO-AlaOa-SiOa... Furnace Dimensions... TVA No. 6 Furnace... Furnace Shell Shapes... Calcium Phosphate Agglomerating Methods Comparative Capital Costs for the Electric Furnace Production of Phosphorus... Influence of Plant Design Capacity, Stream Factor, Electricity Cost, Phosphate Cost, and Coke Cost on the Net Production Cost of Phosphorus... Schematic Representation Comparative Estimated Battery Limits Investments for... Influence of Plant Capacity, Operating Rate, and Phosphorus Price on the Production Cost of Phosphoric Acid from Elemental Phosphorus... Comparative Sulfur and Electricity Costs for Wet Process and Furnace Phosphoric Acids of Equal Net Production Cost... Hourly Heat Distribution for Phosphoric Acid by Way of the Electric Furnace... Blast Furnace Coke Consumption as a Function of the Blast Air Temperature vii

6 ILLUSTRATIONS B.1 B.2 B.3 Hourly Heat Distribution for Phosphoric Acid by Way of the Blast Furnace The M.W. Kellogg Fluidized Bed Phosphorus Process with Circulating Solids for Heat Transfer Two-Stage Phosphate Reduction Process Proposed by Shell International Research Proposed Phosphorus Fuel Furnace Fuel Furnace Heat Flows Comparative Capital Investment and Production Costs for the Fuel Furnace and Wet Process Effect of Plant Capacity on the Production Costs of Hydrogen and Phosphoric Acid Phosphorus Furnace By-Products and Their Potential Applications Heat Content of Phosphorus and the Dissociation of Phosphorus Vapor Vapor Pressures of White Phosphorus and Phosphorus Pentoxide Density and Viscosity of Liquid Phosphorus viii

7 TABLES Summary of Capital and Production Costs for Furnace Phosphorus and Phosphoric Acid Summary of Capital and Operating Costs for the Fuel Furnace Production of Phosphorus Summary of Capital and Production Costs for Phosphoric Acid and Hydrogen by Steam Oxidation of Phosphorus Producers of Elemental Phosphorus in the United States Producers of Elemental Phosphorus Outside of the United States Elemental Phosphorus Consumption in the United States Possible Rectangular Phosphorus Furnace Designs Circular Phosphorus Furnaces Actual and Projected Design Details Estimated Capital and Operating Costs for the Preparation of Phosphorus Furnace Feeds by Various Methods Feed Preparation and Furnace Patents Major Process Equipment and Utilities Summary Stream Flows Fixed Capital Investment Total Capital Investment Production Costs Commercial Plants Operated by TVA Details of Combustion Chambers and Hydrators Major Process Equipment and Utilities Summary Stream Flows , ix

8 Fixed Capital Investment , Total Capital Investment., Production Costs Heat Balance for the Process Capital and Production Costs for Wet Process Phosphoric Acid..., Modified Capital and Operating Costs for the Phosphorus Blast Furnace , Major Process Equipment and Utilities Summary Stream Flows , , Fixed Capital Investment Total Capital Investment Production Costs Major Process Equipment and Utilities Summary Stream Flows Fixed Capital Investment Total Capital Investment Production Costs , , 195 Division of Production Costs Between Phosphoric Acid and Hydrogen...,. 197 X

9 TABLES C.l A Manufacturer's Phosphorus Specifications....., C.2 Analyses of Elemental Phosphorus from U.S. Sources..,., 226 C.3 Food-Grade Phosphoric Acid Specifications (B-12)....,, 226 C.4 Typical Analyses of Food-Grade Phosphoric Acid (10014).., 227 C.5 Analysis of a Technical Grade Phosphoric Acid xi

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