EPA-450/2-77-005 (OAQPS No. 1.2-070) FINAL GUIDELINE DOCUMENT: ;ONTROL OF FLUORIDE EMISSIONS FROM EXISTING PHOSPHATE FERTILIZER PLANTS Emission Standards and Engineering Division U.S. ENVIRONMENTAL PROTECTION ‘AGENCY Office of Air and Waste Management Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 March 1977 This document does not constitute a general endorsement of supplementary control systems as a control alternative. It is intended only to assist the responsible control agencies in those limited situations where legislation, EPA or the courts permit its use. This report is issued by the Environmental Protection Ag,ency to report technical data of interest to a limited number of readers. Copies are available free of charge to Federal employees, current contractors and grantees, and nonprofit organizations - in limited quantities - from the Library Services Office (MD-35)) Research Triangle Park, North Carolina 27711; or, for a fee, from the National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161, Publication No. EPA-450/2-77-005 ii CONTENTS 1. INTRODUCTION AND SUMMARY l-l 1.1 INTRODUCTION l-l 1.2 HEALTH EFFECTS OF FLUORIDES l-5 , 1.3 FLUORIDES AND THEIR CONTROL l-6 1.4 EMISSION GUIDELINES l-7 1.5 COMPLIANCE TIMES l-10 1.6 ASSESSMENTS l-11 1.6.1 Ecdnomic l-11 1.6.2 Environmental l-15 1.6.3 Energy l-16 1.6.4 Inflation l-17 1.7 REFERENCES l-18 2. HEALTH AND WELFARE EFFECTS OF FLUORIDES 2-l 2.1 INTRODUCTION 2-l 2.2 EFFECT OF FLUORIDES ON HUMAN HEALTH 2-3 2.2.1 Atmospheric Fluorides 2-3 2.2.2 Ingested Fluorides 2-3 2.3 EFFECT OF FLUORIDES ON ANIMALS 2-5 2.4 EFFECT OF ATMOSPHERIC FLUORIDES ON 2-6 VEGETATION 2.5 EFFECT OF ATMOSPHERIC FLUORIDES ON 2-7' MATERIALS OF CONSTRUCTION 2.5.1 Etching of Glass 2-7 2.5.2 Effects of Fluorides on Structures . 2-9 2.6 RATIONALE 2-10 2.7 REFERENCES 2-10 iii Page 3. PHOSPHATE FERTILIZER INDUSTRY ECONOMIC PROFILE AND 3-l STATISTICS 3.1 INDUSTRY STRUCTURE 3-l 3.2 EXISTING PLANTS 3-4 3.3 CAPACITY UTILIZATION 3-18 3.4 CONSUMPTIONPATTERNS 3-20 3.5 FUTURE TRENDS 3-25 3.6 PRICES 3-29 3.7 WORLD STATISTICS ON-P205 3-33 3.8 REFERENCES 3-36 4. PHOSPHATE FERTILIZER PROCESSES 4-l 4.1 INTRODUCTION 4-l 4.2 WET-PROCESSPHOSPHORIC ACID MANUFACTURE 4-3 4.3 SUPERPHOSPHORICACID MANUFACTURE 4-11 4.4 DIAMMONIUM PHOSPHATEMANUFACTURE 4-l 7 4.5 TRIPLE SUPERPHOSPHATEMANUFACTURE AND STORAGE 4-21 4.5.1 Run-of-Pile Triple Superphosphate 4-21 Manufacture and Storage 4.5.2 Granular Triple Superphosphate 4-24 Manufacture and Storage 4.6 REFERENCES 4-29 5. EMISSIONS 5-l 5.1 NATURE OF EMISSIONS 5-l 5.2 UNCONTROLLEDFLUORIDE EMISSIONS 5-3 5.2.1 Emissions from Wet-Process Phosphoric 5-3 Acid Manufacture 5.2.2 Emissions from Superphosphoric Acid 5-7 Manufacture iv Page 5.2.3 Emissions from Diammonium Phosphate 5-8 Manufacture 5.2.4 Emissions from Triple Superphosphate 5-10 Manufacture and Storage 5.3 TYPICAL CONTROLLEDFLUORIDE EMISSIONS 5-12 5.3.1 Emissions from Wet-Process Phosphoric 5-12 Acid Plants 5.3.2 Emissions from Superphosphoric Acid 5-13 Manufacture 5.3.3 Emissions from Diammonium Phosphate 5-13 Manufacture 5.3.4 Emissions from Triple Superphosphate 5-13 Manufacture and Storage 5.4 GYPSUM POND EMISSIONS 5-15 5.5 REFERENCES 5-18 6. CONTROL TECH,NIQUES FOR FLUORIDES FROM PHOSPHATE 6-l FERTILIZER PROCESSES 6.1 SPRAY-CROSSFLOWPACKED BED SCRUBBER 6-l 6.1.1 Description 6-l 6.1.2 Emission Reduction 6-5 6.1.3 Retrofit Costs for Spray-Crossflow 6-7 Packed Bed Scrubbers 6.2 VENTURI SCRUBBER 6-71 6.2.1 Description 6-71 6.2.2 Emission Reduction 6-74 6.2.3 Retrofit Costs for Venturi Scrubbers 6-75 6.3 SPRAY TOWER SCRUBBER 6-78 6.3.1 Description 6-7: 6.3.2 Emission Reduction 6-78 V Page 6.3.3 Retrofit Costs for Cyclonic Spray Towers 6-79 6.4 IMPINGEMENT SCRUBBER 6-86 6.5 SUMMARYOF CONTROLOPTIONS 6-87 6.6 DESIGN, INSTALLATION, AND STARTUP TIMES 6-88 6.7 REFERENCES 6-95 7. ECONOMIC IMPACT 7-l 7.1 INTRODUCTION 7-l 7.2 IMPACT ON MODEL PLANTS 7-2 7.3 CRITERIA FOR PLANT CLOSURES 7-4 7.4 IMPACT ON THE INDUSTRY 7-6 7.5 IMPACT ON EMPLOYMENTAND COMMUNITIES 7-10 7.6 SUMMARY 7-10 7.7 REFERENCES 7-12 8. B4ISSZON GUIDELINES FOR EXISTING 8-l PHOSPHATE FERTILIZER PLANTS 8.1 GENERAL RATIONALE 8-l 8.2 EVALUATION OF INDIVIDUAL EMISSION GUIDELiNES 8-4 8.2.1 Wet-Process Phosphoric Acid Plants 8-4 8.2.2 Superphosphoric Acid Plants 8-6 8.2.3 Diarrvnonium Phosphate Plants 8-7 8.2.4 Run-of-Pile Triple Superphosphate Production 8-8 and Storage Facilities 8.2.5 Granular Triple Superphosphate Production 8-9 Facilities 8.2.6 Granular Triple Superphosphate Storage 8-11 Facilities 853 REFERENCES 8-13 vi Sage 9. ENVIRONMENTALASSESSMENT 9-l 9.1 ENVIRONMENTALASSESSMENT OF THE EMISSION 9-l GUIDELINES 9.1.1 Air 9-l 9.1.1.1 Atmospheric Dispersion of Fluoride Emissions 9-4 9.1.1.2 Emission Guideline vs. a Typical Standard 9-9 9.1.2 Water Pollution 9-9 9.1.3 Solid Waste Disposal 9-12 9.1.4 Energy 9-13 . 9.1.5 Other Environmental Concerns 9-18 9.2 ENVIRONMENTALASSESSMENT OF ALTERNATIVE 9-18 EMISSI.ON CONTROLSYSTEMS 9.3 SOCIO-ECONOMIC EFFECTS 9-19 '9:q REFERENCES 9-20 vii LIST OF FIGURES Figure Page 3-l Wet-Process and Superphosphoric Acid Plant Locations 3-16 3-2 Triple Superphosphate and Ammonium Phosphate Plant 3-17 Locations 3-3 Capacity Utilization of Wet-Process Phosphoric Acid 3-21 3-4 Capacity Utilization of Arrunonium Phosphates 3-22 3-5 Wholesale Prices for Triple Superphosphate and 3-31 Diammonium Phosphate 4-l Major Phosphate Rock Processing Steps 4-2 4-2 Flow Diagram Illustrating a Wet-Process Phosphoric 4-5 Acid Plant 4-3 Flow Diagram for Prayon Reactor 4-6 4-4 Operating Cycle of Rotary Horizontal Tilting 4-9 Pan Filter 4-5 TVA Evaporator for Producing Superphosphoric Acid 4-13 4-6 Submerged Combustion Process for Producing Super- 4-14 phosphoric Acid 4-7 Stauffer Evaporator Process 4-16 4-8 Swenson Evaporator Process 4-16 4-9 TVA Diammonium Phosphate Process 4-19 4-10 Run-of-Pile Triple Superphosphate Production and 4-22 Storage 4-11 TVA Cone Mixer 4-23 4-12 TVA One-Step Process for Granular Triple Super- 4-25 phosphate 4-13 Dorr-Oliver Slurry Granulation Process for Triple 4-27 Superphosphate 4-14 Granular Triple Superphosphate Storage 4-28 viii pi.,!,,- i j . Fiqure Page 6-l Spray-Crossflow Packed Bed Scrubber 6-2 6-2 Manufacture of Wet-Process Phosphoric Acid 6-15 6-3 Existing Control Equipment Layout for Model WPPA Plant 6-17 6-4 Retrofit Control Equipment Layout for Model WPPA Plant 6-20 6-5 Retrofit Control Equipment Layout for Model SPA Plant 6-31 6-6 Existing Control Equipment Layout for Model DAP Plant 6-38 6-7 Retrofit Control Equipment Layout for Model DAP Plant 6-39 6-8 Existing Control Equipment Layout for Mode 1 ROP-TSP 6-47 Plant, Case A 6-9 Retrofit Control Equipment Layout for Mode 1 ROP-TSP 6-51 Plant, Case B 6-10 Existing Control Equipment Layout for Model GTSP 6-58 Plant 6-11 Retrofit Control Equipment Layout for Model GTSP 6-59 Plant ' 6-12 Gas Actuated Venturi Scrubber with Cyclonic Mist 6-73 Eliminator 6-13 Water Actuated Venturi 6-73 6-14 Cyclonic Spray Tower Scrubber 6-79 6-15 Retrofit Control Equipment Layout for Model ROP-TSP Plant 6-82 6-16 Doyle Scrubber 6-86 6-17 Time Schedule for the Installation of a Wet Scrubber on 6-89 a Wet-Process Phosphoric Acid Plant ix LIST OF TABLES Table Page -. _ _.___ __.. -- ------ ,.. .-. l-l Fluoride Emission Guidelines for i-a- Existing Phosphate Fertilizer Manufacturi-ng Plan,ts.- l-2 Performance of Aqueous Scrubber Emission Control -1-9 Equipment in Phosphate Fertilizer Manufacturinq Plants _ ., . ..-_. _ l-3 Increments of Progress for Installation of Wet 7 -TO Scrubber for a Wet Process Phosphoric Acid Plant -~ ' . .I v. l-4 Economic Impact of Fluoride Emission Guidelines for l-12 Existing Phosphate Fertilizer Manufacturing Facilities l&5 Summary of Retrofit Control Cost Requirements for Various Phosphate Fertilizer Manufacturing Processes 2-l Examples of HF Concentrations (PPB) and Exposure Durations Reported to Cause Lea+ Damage and Poten- tial Reduction in Crop Values 3-l Ten Largest Phosphate Rock Producers 3-2 3-2 Ten Largest Phosphoric Acid Producers 3-3 3-3 Production Capacity of Wet-Process Phosphoric 3-5 Acid (1973) 3-4 Produetion Capacity of Superphosphoric Acid (1973) 3-8 3-5 Production Capacity of Triple Superphosphate (1973) 3-10 3-6 Production Capacity of Ammonium Phosphates (1973) 3-12 3-7 Production as Percent of Capacity 3-19 3-8 U.S. Phosphate Consumption, 1960-1973 (1000 tons 3-24 '2'5) 3-9 U.S. Production of Three Commodities in the Phosphate 3-26 Industry, 1950-1973 3-10 Swwary of List Prices as of July 1974 and Basis 3-32 for Quotation 3-11 United States and World Consumption of Phosphate 3-34 Fertilizer 3-12 World Reserves of Phosphate Rock and Apatite 3-35 X Page P205 Content of Phosphate Fertilizers 4-3 Components of Typical Wet-Process Acid 4-10 Comparison of Orthophosphoric to Superphosphoric 4-11 Acid Fluoride Emissions from an Uncontrolled Wet-Process 5-4 Phosphoric Acid Plant Typical k'iaterial Balance of Fluoride in Manufacture 5-6 of Wet-Process Phosphoric Acid ;.