Phosphoric
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June 9, 2025, 1:33 PM
1.Chemical and Physical Properties
1.1 Chemical Identity
- Common Name: Phosphoric Acid (Orthophosphoric Acid is the most common form)
- Chemical Name (IUPAC): Orthophosphoric Acid (commonly referred to simply as Phosphoric Acid)
- CAS Registry Number: 7664-38-2
- Chemical Class: Mineral acid, inorganic acid.
- Molecular Formula: H₃PO₄
- Molecular Weight: 98.00 g/mol
- Other Forms:
- Besides orthophosphoric acid, there are other phosphoric acids, like pyrophosphoric acid (H₄P₂O₇) and triphosphoric acid (H₅P₃O₁₀), which are essentially oligomers of orthophosphoric acid. However, "phosphoric acid" typically refers to orthophosphoric acid.
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1.2 Key Physical Properties (Orthophosphoric Acid)
- Appearance:
- Pure anhydrous form: White crystalline solid.
- Common commercial form: Colorless, odorless, viscous syrupy liquid (typically aqueous solutions of 85% or 75%).
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- Melting Point: 42.35°C (for anhydrous solid). Aqueous solutions have lower freezing points.
- Boiling Point: Decomposes at higher temperatures (above 213°C, loses water to form pyrophosphoric acid). Common 85% solution boils around 158°C.
- Density:
- Anhydrous solid: Approximately 1.83 - 1.88 g/cm³
- 85% aqueous solution: Approximately 1.685 g/cm³ at 25°C.
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- Solubility: Miscible with water in all proportions. Soluble in ethanol.
1.3 Key Chemical Properties
- Acidity: Phosphoric acid is a triprotic acid, meaning it can donate three protons (H⁺ ions) in successive steps.
- pKa1 = 2.15 (H₃PO₄ ⇌ H₂PO₄⁻ + H⁺)
- pKa2 = 7.20 (H₂PO₄⁻ ⇌ HPO₄²⁻ + H⁺)
- pKa3 = 12.37 (HPO₄²⁻ ⇌ PO₄³⁻ + H⁺)
- It is a moderately strong acid for the first dissociation, and a weak acid for the second and third.
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- Reactivity:
- Reacts with bases to form phosphate salts (dihydrogen phosphates, hydrogen phosphates, and phosphates).
- Reacts with active metals (e.g., zinc, iron) to produce hydrogen gas and phosphate salts.
- Can act as a dehydrating agent at high concentrations and temperatures.
- Can polymerize upon heating to form polyphosphoric acids.
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- Corrosivity:
- Corrosive to many metals, especially at higher concentrations and temperatures. Less corrosive than strong acids like sulfuric or hydrochloric acid at similar concentrations.
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2.Production Technologies
2.1 Major Production Processes
- Wet Process (WPPA - Wet Process Phosphoric Acid):
- Most common method for fertilizer-grade phosphoric acid production (often called "green acid" or "merchant grade acid").
- Involves reacting phosphate rock (primarily calcium phosphate, e.g., apatite) with sulfuric acid.
- Reaction: Ca₅(PO₄)₃F (fluorapatite) + 5H₂SO₄ + 10H₂O → 3H₃PO₄ + 5(CaSO₄·2H₂O) (gypsum) + HF
- Produces dilute and impure acid (typically 28-32% P₂O₅), which is then concentrated (to 40-55% P₂O₅) and may undergo some purification.
- Generates large quantities of phosphogypsum as a byproduct, which poses disposal challenges.
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- Thermal Process (TPPA - Thermal Process Phosphoric Acid):
- Produces a much purer, food-grade or technical-grade phosphoric acid.
- Elemental phosphorus (P₄) is burned in air to produce phosphorus pentoxide (P₂O₅).
- P₄ + 5O₂ → P₄O₁₀ (or 2P₂O₅)
- Phosphorus pentoxide is then hydrated with water to form phosphoric acid.
- P₄O₁₀ + 6H₂O → 4H₃PO₄
- This process is more energy-intensive and expensive than the wet process, due to the initial production of elemental phosphorus in an electric furnace.
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2.2 Raw Materials
- Wet Process:
- Phosphate Rock (various grades of apatite)
- Sulfuric Acid (H₂SO₄)
- Water
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- Thermal Process:
- Elemental Phosphorus (P₄) - produced from phosphate rock, coke, and silica in an electric furnace.
- Air (Oxygen)
- Water (often highly purified for food grade)
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2.3 Purification and Concentration
- Wet Process Acid:
- Concentration: Typically by evaporation to increase P₂O₅ content (e.g., from ~30% to ~54% P₂O₅, which is about 75% H₃PO₄).
- Purification: May involve solvent extraction (e.g., with MIBK or TBP) to remove impurities like heavy metals, arsenic, fluorine, and organic matter, especially if a higher grade (e.g., technical grade) is required. Defluorination is a common step.
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- Thermal Process Acid:
- Generally yields a high-purity acid directly. Further purification steps are minimal but may include treatment with activated carbon or ion exchange for very high purity applications (e.g., food, pharmaceutical).
- Concentration is controlled by the amount of water used in hydration.
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2.4 Grades of Phosphoric Acid
- Fertilizer Grade (Agricultural Grade):
- Produced by the wet process, less pure, used primarily for phosphate fertilizer production (e.g., DAP, MAP, TSP). Typically 40-55% P₂O₅.
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- Technical Grade:
- Purer than fertilizer grade, can be made by purifying wet process acid or by the thermal process. Used in metal treatment, catalysts, refractories, etc.
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- Food Grade:
- High purity, produced by the thermal process or highly purified wet process acid. Meets stringent standards for use in food and beverages. Typically 75% or 85% H₃PO₄ solutions.
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- Pharma Grade:
- Highest purity, used in pharmaceutical preparations. Meets pharmacopoeial standards.
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3.Applications
3.1 Fertilizers (Largest Use)
- Primary Application:
- Over 80-90% of global phosphoric acid production is used to manufacture phosphate fertilizers.
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- Key Products:
- Diammonium Phosphate (DAP)
- Monoammonium Phosphate (MAP)
- Triple Superphosphate (TSP)
- Ammonium Polyphosphate (APP) liquid fertilizers
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- Role:
- Provides phosphorus, an essential macronutrient for plant growth, vital for root development, flowering, fruiting, and energy transfer.
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3.2 Food and Beverage Industry
- Acidulant:
- Adds a tangy or sour taste to soft drinks (especially colas, e.g., E338), jams, jellies, and processed foods.
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- pH Control:
- Used to adjust and stabilize pH in various food products.
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- Buffering Agent:
- Phosphate salts derived from phosphoric acid are used as buffering agents.
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- Sequestrant:
- Can bind metal ions, preventing discoloration or spoilage in some food products.
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- Yeast Nutrient:
- In baking and brewing.
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3.3 Industrial and Technical Applications
- Metal Treatment:
- Rust Removal: Converts iron oxide (rust) to iron phosphate, which can be scrubbed off or provide a passivation layer.
- Phosphating/Parkerizing: Creates a phosphate conversion coating on steel surfaces for corrosion resistance and improved paint adhesion.
- Metal Cleaning and Etching: Used in electropolishing and chemical polishing of metals like aluminum.
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- Catalyst:
- Used as an acid catalyst in some chemical reactions (e.g., alkylation, polymerization).
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- Water Treatment:
- Phosphate compounds are used for scale and corrosion control in water systems.
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- Detergents:
- Sodium tripolyphosphate (STPP), derived from phosphoric acid, was historically a major component of detergents as a water softener and builder, though its use has declined due to environmental concerns (eutrophication)
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3.4 Other Niche Applications
- Dental Products:
- Used in dental cements, etchants for preparing tooth surfaces for bonding, and some teeth whitening products.
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- Pharmaceuticals:
- As an excipient, pH adjuster, or in the synthesis of phosphate-containing drugs.
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- Electronics:
- Used in semiconductor processing as an etchant.
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- Refractories:
- As a binder in refractory materials.
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- Activated Carbon Production:
- As a chemical activating agent.
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- Electrolyte:
- In some phosphoric acid fuel cells (PAFCs).
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4.Market Analysis
4.1 Global Market Overview
- Size & Growth:
- A very large commodity chemical market, primarily driven by the fertilizer industry. The market size is valued in the tens of billions of USD annually. Growth is generally tied to agricultural output, population growth, and dietary changes.
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- Production Dominance:
- Wet process phosphoric acid for fertilizers dominates production volume. Thermal process acid is a smaller, higher-value segment.
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- Key Metrics:
- Market often discussed in terms of P₂O₅ equivalent.
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4.2 Key Market Dynamics
- Drivers:
- Growing global population and increasing food demand, driving fertilizer consumption.
- Improving agricultural practices in developing countries.
- Demand for processed foods and beverages (for food-grade acid).
- Industrial applications in metal treatment and other sectors.
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- Restraints:
- Environmental concerns related to phosphogypsum disposal from the wet process.
- Eutrophication concerns from phosphate runoff in agriculture, leading to regulations on fertilizer use in some regions.
- Fluctuating raw material costs (phosphate rock, sulfur for sulfuric acid).
- Energy costs, especially for the thermal process.
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4.3 Regional Demand and Production
- Major Producing Regions:
- Regions with significant phosphate rock reserves and fertilizer industries are major producers, including China, USA, Morocco, Russia, and India.
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- Major Consuming Regions:
- Regions with large agricultural sectors are major consumers, aligning with production but also including major food importers. Asia (China, India) is a dominant consuming region.
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- Trade:
- Significant international trade in phosphoric acid (especially merchant grade) and phosphate fertilizers.
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5.Upstream and Downstream Linkages
5.1 Upstream Linkages (Inputs for Production)
- Raw Materials Sourcing:
- Phosphate Rock: Mining and beneficiation of phosphate rock are crucial upstream activities. Major deposits are found in North Africa, China, USA, and the Middle East.
- Sulfur: For sulfuric acid production (primarily from petroleum refining, natural gas processing, or elemental sulfur mining).
- Elemental Phosphorus: For thermal process, produced from phosphate rock, coke, and silica in energy-intensive electric furnaces.
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- Energy:
- Significant energy input for mining, sulfuric acid production, elemental phosphorus production (thermal process), and acid concentration.
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5.2 Downstream Linkages (outputs and consumers)
- Fertilizer Industry:
- The largest downstream consumer, producing DAP, MAP, TSP, etc.
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- Food and Beverage Industry: Consumes food-grade phosphoric acid as an additive.
- Chemical Industry:
- Uses phosphoric acid as a raw material for producing various phosphate salts and chemicals (e.g., STPP, sodium phosphates, calcium phosphates for animal feed).
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- Metal Treatment and Industrial Sector:
- Consumes technical grade acid for various surface treatment and cleaning applications.
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- Distribution:
- Involves bulk transport (ships, rail, trucks) for industrial/fertilizer grades and specialized packaging for food/pharma grades.
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