Section Phosphoric Acid Table of Contents A Report by NexantThinking Process Evaluation/Research Planning (PERP) Program PERP Report 2015S10 Published September 2015 Page 1 Executive Summary... 1 1.1 INTRODUCTION... 1 1.2 TECHNOLOGY OVERVIEW... 2 1.2.1 CHEMISTRY... 2 1.2.2 Technology Holders and Licensing Status... 4 1.3 PURIFICATION METHODS USED IN THE WET PROCESS... 6 1.4 STRATEGIC AND BUSINESS CONSIDERATIONS... 7 1.5 PRODUCTION COST ESTIMATES... 8 1.6 COMMERCIAL APPLICATIONS... 12 1.7 REGIONAL MARKET ANALYSIS... 13 2 Introduction... 14 2.1 BACKGROUND... 14 2.2 VALUE CHAIN... 15 2.3 TECHNOLOGY REVIEW... 15 2.3.1 Wet Process Overview... 15 2.3.2 Thermal Process Overview... 37 2.3.3 Superphosphoric Acid... 41 2.4 TECHNOLOGY DEVELOPMENTS... 42 2.5 TECHNOLOGY HOLDER AND LICENSING STATUS... 43 2.6 STRATEGIC AND BUSINESS CONSIDERATIONS... 43 2.7 PHYSICAL AND THERMODYNAMIC PROPERTIES... 44 2.8 SPECIFICATIONS... 48 2.9 HEALTH HAZARDS... 49 2.10 STORAGE, HANDLING, AND TRANSPORTATION... 49 3 Commercial Technologies... 50 1
3.1 INTRODUCTION... 50 3.2 ECOPHOS... 51 3.2.1 Background... 51 3.2.2 Technology Features... 51 3.2.3 Process Description... 52 3.3 JACOBS ENGINEERING... 55 3.3.1 Background... 55 3.3.2 Technology Features... 56 3.3.3 Process Description... 56 3.4 PRAYON... 60 3.4.1 Background... 60 3.4.2 Technology Features... 60 3.4.3 Typical Process Description for the Mark IV Dihydrate Prayon Process (DPP)... 68 3.5 Technip... 72 3.5.1 Background... 72 3.5.2 Technology Features... 72 3.5.3 Process Description... 74 4 Purification Methods Utilized in the Wet Process... 90 4.1 SOLVENT EXTRACTION PROCESSES... 91 4.1.1 Albright & Wilson Purification Process... 91 4.1.2 Israel Mining Industries (IMI) Purification Process... 93 4.1.3 Prayon Purification Process... 96 4.1.4 Rhône-Poulenc Purification Process... 96 4.2 URANIUM RECOVERY... 99 4.3 REMOVAL OF HEAVY METALS (INCLUDING CADMIUM)... 100 5 Developing Technologies... 101 5.1 INTRODUCTION... 101 5.2 SELECTED RECENT PATENTS... 101 5.3 THE IMPROVED HARD PROCESS/KILN PHOSPHORIC ACID PROCESS... 104 6 Process Economics... 107 6.1 COSTING BASIS... 107 6.1.1 Investment Basis... 107 6.1.2 Pricing Basis... 107 6.1.3 Cost of Production Basis... 108 2
6.2 COST OF PRODUCING CONCENTRATED WET PHOSPHORIC ACID VIA A CONVENTIONAL DIHYDRATE PROCESS... 109 6.2.1 United States Gulf Coast... 109 6.2.2 China... 109 6.2.3 Middle East... 109 6.2.4 Comparative Economics for Conventional Dihydrate Processes... 113 6.3 COST OF PRODUCING CONCENTRATED WET PHOSPHORIC ACID VIA A CONVENTIONAL HEMIHYDRATE PROCESS... 114 6.3.1 United States Gulf Coast... 114 6.3.2 China... 114 6.3.3 Middle East... 114 6.3.4 Comparative Economics for Conventional Hemihydrate Processes... 118 6.4 COST OF PRODUCING PURIFIED WET PHOSPHORIC ACID VIA A CONVENTIONAL SOLVENT EXTRACTION PROCESS... 119 6.4.1 U.S. Gulf Coast... 119 6.4.2 China... 119 6.4.3 Middle East... 123 6.4.4 Comparative Economics for Conventional Purified Wet Phosphoric Acid Processes... 123 6.5 COST OF PRODUCING THERMAL PHOSPHORIC ACID VIA A CONVENTIONAL ELECTRIC FURNACE PROCESS... 124 6.5.1 United States Gulf Coast... 124 6.5.2 China... 128 6.5.3 Middle East... 128 6.5.4 Comparative Economics for Conventional Thermal Phosphoric Acid Processes... 128 6.6 COMPARISON OF COMMERCIAL PROCESSES TO PRODUCE PHOSPHORIC ACID... 130 7 Commercial Applications... 136 7.1 INTRODUCTION... 136 7.2 PHOSPHATE FERTILIZERS... 139 7.2.1 Granular Ammonium Phosphates... 139 7.2.2 Ammonium Polyphosphates and Liquid Fertilizers... 140 7.2.3 MAP Powders and Mini-Granules... 140 7.2.4 Superphosphates... 140 7.3 INDUSTRIAL PHOSPHATES... 140 7.3.1 Detergents and Cleaners... 141 3
7.3.2 Water Treatment... 142 7.3.3 Food-Grade Uses... 142 7.3.4 Metal Finishing... 142 7.3.5 Animal Feedstuffs... 143 7.3.6 Other Uses of Industrial Phosphates... 143 7.4 OTHER USES OF PHOSPHORIC ACID... 144 8 Regional Market Analysis... 145 8.1 NORTH AMERICA... 145 8.1.1 Demand... 145 8.1.2 Supply... 145 8.1.3 Supply, Demand, and Trade... 146 8.2 WESTERN EUROPE... 148 8.2.1 Demand... 148 8.2.2 Supply... 148 8.2.3 Supply, Demand, and Trade... 148 8.3 ASIA PACIFIC... 149 8.3.1 Demand... 149 8.3.2 Supply... 150 8.3.3 Supply, Demand, and Trade... 150 9 Glossary... 152 10 References... 154 Appendix Page A Phosphate Rock... A-1 B PERP Program Title Index (2006-2015)... B-1 4
Figure Page 1.1 U.S. Gulf Coast Summary of Phosphoric Acid Costs... 9 1.2 Chinese Summary of Phosphoric Acid Costs... 10 1.3 Middle Eastern Summary of Phosphoric Acid Costs... 11 1.4 Global Phosphoric Acid Demand by End-Use, 2014... 13 2.1 Phosphate Fertilizer Block Flow Diagram... 16 2.2 Correlation between Calcium Sulfate Hydrate Crystals and Temperature... 18 2.3 Transitions for System CaSO4-H3PO4-H2O... 19 2.4 Flow Diagram of the Dihydrate Wet Phosphoric Acid Process... 26 2.5 Equipment Associated with a Phosphoric Acid Filter... 29 2.6 Flow Diagram of the Hemihydrate Wet Phosphoric Acid Process... 31 2.7 Flow Diagram of the Hemi-dihydrate Recrystallization Process Single Stage Filtration... 34 2.8 Flow Diagram of the Hemi-dihydrate Recrystallization Process Double Stage Filtration.. 35 2.9 Flow Diagram of the Di-Hemihydrate Recrystallization Process Double Stage Filtration... 36 2.10 Flow Diagram of the Thermal Phosphoric Acid Process... 40 2.11 Phosphoric Acid-Water Solid-Liquid Phase Diagram... 45 2.12 Phosphoric Acid-Water Liquid-Vapor Phase Diagram... 46 2.13 Density of Phosphoric Acid as Function of Concentration and Temperature... 46 2.14 Viscosity of Phosphoric Acid as Function of Concentration and Temperature... 47 2.15 Specific Heat of Phosphoric Acid as Function of Concentration and Temperature... 47 3.1 EcoPhos Process for Phosphoric Acid... 53 3.2 EcoPhos Purification... 54 3.3 Jacobs Reactor System... 55 3.4 Jacobs Phosphoric Acid Process... 57 3.5 Jacobs Concentration Process... 59 3.6 Mark IV Dihydrate Prayon Process (DPP)... 62 3.7 Central Prayon Process (CPP)... 63 3.8 Prayon Hemihydrate One-crystal Process (PH1)... 65 3.9 Prayon Hemihydrate Two-crystal Process (PH2)... 66 3.10 Prayon Hemihydrate Three-crystal Process (PH3)... 67 3.11 Prayon Mark IV Reactor System... 69 3.12 Flow Scheme for the Production of Phosphoric Acid via Technip Process... 73 3.13 Technip Phosphoric Acid Single Tank Air Cooled Process... 75 3.14 Technip Single Tank... 76 3.15 P2O5 Losses at Reaction Stage versus Free Sulfate in Reactor Slurry... 77 5
3.16 Technip Large Capacity Flash Cooled Reaction System... 80 3.17 Technip UCEGO Filter... 81 3.18 Technip Filtration Unit... 84 3.19 Technip Concentration Unit... 86 4.1 Block Diagram of A & W Purification Process;... 92 4.2 Block Flow Diagram of PCS Aurora... 94 4.3 Block Diagram of IMI Purification Process... 95 4.4 Block Diagram of Prayon Purification Process... 97 4.5 Block Diagram of R-P Purification Process... 98 5.1 Block Diagram for the Production of Phosphoric Acid... 102 5.2 Block Diagram for the Production of Phosphoric Acid... 103 5.3 JDC s Unit Costs versus Volume Chart for IHP... 105 5.4 Block Flow Diagram for the Production of Phosphorus Pentoxide in a Kiln Rotary Bed (U.S. 7 378 070 B2)... 106 6.1 Summary of Concentrated Wet Phosphoric Acid (54 Percent P2O5) via a Conventional Dihydrate Process... 113 6.2 Summary of Concentrated Wet Phosphoric Acid (54 Percent P2O5) via a Conventional Hemihydrate Process... 118 6.3 Summary of Purified Wet Phosphoric Acid (62 percent P2O5) via a Conventional Solvent Extraction Process... 124 6.4 Summary of Thermal Phosphoric Acid (54 76 Percent P2O5) via a Conventional Electric Furnace Process... 129 6.5 U.S. Gulf Coast Summary of Phosphoric Acid Costs... 131 6.6 Chinese Summary of Phosphoric Acid Costs... 133 6.7 Middle Eastern Summary of Phosphoric Acid Costs... 134 7.1 Phosphate Fertilizer Block Flow Diagram... 137 8.1 Global Phosphoric Acid Demand by End-Use, 2014... 145 8.2 North America Phosphoric Acid Supply, Demand, and Trade... 147 8.3 Western Europe Phosphoric Acid Supply, Demand, and Trade... 149 8.4 Asia Pacific Phosphoric Acid Supply, Demand, and Trade... 151 6
Table Page 1.1 Phosphoric Acid Technology Licensors... 4 1.2 Phosphoric Acid Purification Process... 6 1.3 Strategic/Business Considerations... 7 1.4 U.S. Gulf Coast Summary of Phosphoric Acid Process Economics... 8 1.5 Chinese Summary of Phosphoric Acid Process Economics... 9 1.6 Middle Eastern Summary of Phosphoric Acid Process Economics... 10 2.1 Typical Merchant Wet Phosphoric Acid Composition... 19 2.2 Origin and Composition of Different Phosphate Rocks... 22 2.3 Trace Elements of Different Phosphate Rocks... 23 2.4 Distribution of Fluoride in Production of Wet Phosphoric Acid... 25 2.5 Advantages and Disadvantages of the Dihydrate Process... 27 2.6 Typical Thermal Phosphoric Acid Composition... 38 2.7 Typical Phosphorus Slag Composition... 39 2.8 Phosphoric Acid Technology Licensors... 43 2.9 Strategic/Business Considerations... 43 2.10 Key Physical and Chemical Properties of Phosphoric Acid... 45 2.11 Typical Specifications for Phosphoric Acid... 48 3.1 Jacobs Phosphoric Acid Process Specification... 56 3.2 Jacobs Product Specifications... 58 3.3 Characteristics of Prayon s Technologies... 61 3.4 UCEGO Filter Sizes... 82 3.5 Technip Typical Operating Data... 89 4.1 Phosphoric Acid Purification Process... 90 4.2 Cadmium Levels in Phosphoric Acid... 100 6.1 Prices of Raw Materials, Products, Utilities, and Labor... 108 6.2 Cost of Production Estimate for: Concentrated Wet Phosphoric Acid (54 Percent P2O5) Process: Conventional Dihydrate; USGC Basis... 110 6.3 Cost of Production Estimate for: Concentrated Wet Phosphoric Acid (54 Percent P2O5) Process: Conventional Dihydrate; China Basis... 111 6.4 Cost of Production Estimate for: Concentrated Wet Phosphoric Acid (54 Percent P2O5) Process: Conventional Dihydrate; Middle East Basis... 112 6.5 Summary of Concentrated Wet Phosphoric Acid (54 Percent P2O5) via a Conventional Dihydrate Process... 113 6.6 Cost of Production Estimate for: Concentrated Wet Phosphoric Acid (54 Percent P2O5) Process: Conventional Hemihydrate; USGC Basis... 115 7
6.7 Cost of Production Estimate for: Concentrated Wet Phosphoric Acid (54 Percent P2O5) Process: Conventional Hemihydrate; China Basis... 116 6.8 Cost of Production Estimate for: Concentrated Wet Phosphoric Acid (54 Percent P2O5) Process: Conventional Hemihydrate; Middle East Basis... 117 6.9 Summary of Concentrated Wet Phosphoric Acid (54 Percent P2O5) via a Conventional Hemihydrate Process... 118 6.10 Cost of Production Estimate for: Purified Wet Phosphoric Acid (62 Percent P2O5) Process: Conventional Solvent Extraction; USGC Basis... 120 6.11 Cost of Production Estimate for: Purified Wet Phosphoric Acid (62 Percent P2O5) Process: Conventional Solvent Extraction; China Basis... 121 6.12 Cost of Production Estimate for: Purified Wet Phosphoric Acid (62 Percent P2O5) Process: Conventional Solvent Extraction; Middle East Basis... 122 6.13 Summary of Purified Wet Phosphoric Acid (62 percent P2O5) via a Conventional Solvent Extraction Process... 123 6.14 Cost of Production Estimate for: Thermal Phosphoric Acid (54 76 Percent P2O5) Process: Conventional Electric Furnace; USGC Basis... 125 6.15 Cost of Production Estimate for: Thermal Phosphoric Acid (54 76 Percent P2O5) Process: Conventional Electric Furnace; China Basis... 126 6.16 Cost of Production Estimate for: Thermal Phosphoric Acid (54 76 Percent P2O5)... 127 6.17 Summary of Thermal Phosphoric Acid (54 76 Percent P2O5) via a Conventional Electric Furnace Process... 129 6.18 U.S. Gulf Coast Summary of Phosphoric Acid Process Economics... 130 6.19 Chinese Summary of Phosphoric Acid Process Economics... 132 6.20 Middle Eastern Summary of Phosphoric Acid Process Economics... 134 7.1 Compounds in Phosphate Fertilizer... 136 7.2 Industrial Phosphate Derivatives Tree... 138 7.3 Phosphorus Requirements of Poultry... 144 8.1 North America Phosphoric Acid Capacity, 2014... 146 8.2 North America Phosphoric Acid Supply, Demand, and Trade... 147 8.3 Western Europe Phosphoric Acid Capacity, 2014... 148 8.4 Western Europe Phosphoric Acid Supply, Demand, and Trade... 149 8.5 Asia Pacific Phosphoric Acid Capacity, 2014... 150 8.6 Asia Pacific Phosphoric Acid Supply, Demand, and Trade... 151 8
Nexant Thinking Process Evaluation/Research Planning The NexantThinking Process Evaluation/Research Planning (PERP) program is recognized globally as the industry standard source for information relevant to the chemical process and refining industries. PERP reports are available as a subscription program or on a single report basis. Contact Details: New York: Marcos Nogueira Cesar, Vice President, Global Products, E&CA: Nexant Thinking Phone: + 1-914-609-0324, e-mail: mcesar@nexant.com New York: Heidi Junker Coleman, Global Programs Support Manager Phone: + 1-914-609-0381, e-mail: hcoleman@nexant.com Nexant, Inc. (www.nexant.com) is a leading management consultancy to the global energy, chemical, and related industries. For over 38 years, Nexant has helped clients increase business value through assistance in all aspects of business strategy, including business intelligence, project feasibility and implementation, operational improvement, portfolio planning, and growth through M&A activities. Nexant has its main offices in San Francisco (California), White Plains (New York), and London (UK), and satellite offices worldwide. Copyright by Nexant Inc. 2015. All Rights Reserved. 9