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1 Overview of Phosphate Ore Phosphate ores in nature are mainly classified into apatite-type (e.g., fluorapatite Ca₅(PO₄)₃F) and sedimentary phosphorite (e.g., collophanite). Due to significant variations in raw ore grades (P₂O₅ content ranging from 5% to 40%), beneficiation processes are typically required to enhance the grade to meet industrial standards (P₂O₅ ≥ 30%). Phosphate ores are rich in phosphorus, primarily used for extracting phosphorus and producing related chemical products, such as widely known phosphate fertilizers, as well as common industrial chemicals like yellow phosphorus and red phosphorus. These phosphorus-based materials, derived from phosphate ores, find extensive applications in agriculture, food, medicine, chemicals, textiles, glass, ceramics, and other industries. Given the generally high floatability of phosphate ores, flotation is the most commonly employed beneficiation method.       2 Phosphate Ore Beneficiation Methods   The selection of phosphate ore beneficiation processes depends on ore type, mineral composition, and dissemination characteristics. The primary methods include: Scrubbing and desliming, Gravity separation, Flotation, Magnetic separation, Chemical beneficiation, Photoelectric sorting, and Combined processes. 2.1 Scrubbing and Desliming Process This method is particularly suitable for heavily weathered phosphate ores with high clay content (such as certain sedimentary phosphorites). The technological process consists of: Crushing and Screening: Raw ore is crushed to appropriate particle size (e.g., below 20mm) Scrubbing: Employing scrubbers (like trough scrubbers) with water agitation to separate clay and fine slimes Desliming: Using hydrocyclones or spiral classifiers to remove slime particles smaller than 0.074mm Advantages: Features simple operation and low cost, capable of increasing P₂O₅ grade by 2-5% Limitations: Shows limited effectiveness for processing ores with closely intergrown minerals 2.2 Gravity Separation This method is applicable to ores where phosphate minerals and gangue exhibit significant density differences (e.g., apatite-quartz associations). Commonly used equipment includes: Jigging Machines: Ideal for processing coarse-grained ore (+0.5mm) Spiral Concentrators: Effective for medium-fine particle separation (0.1-0.5mm) Shaking Tables: Specialized for precision separation Advantages: Chemical-free process, making it particularly suitable for water-scarce regions Limitations: Relatively lower recovery rates (approximately 60-70%); Ineffective for processing ultra-fine particle ores 2.3 Flotation Method The most widely applied beneficiation technology for phosphate ores, particularly effective for processing: Low-grade collophanite ores, Complex disseminated ore types 2.3.1 Direct Flotation (Phosphate Mineral Flotation) Reagent Scheme: Collector: Fatty acids (e.g., oleic acid, oxidized paraffin soap) Depressant: Sodium silicate (for silicate depression), starch (for carbonate depression) pH Modifier: Sodium carbonate (adjusting pH to 9-10) Process Flow: ①Grind ore to 70-80% passing 0.074mm ②Condition pulp sequentially with depressants and collectors ③Float phosphate minerals ④Dewater concentrates to obtain final product Applicable Ore Type: Siliceous phosphate ore (phosphate-quartz association) 2.3.2 Reverse Flotation (Gangue Mineral Flotation) Reagent Scheme: Collector: Amine compounds (e.g., dodecylamine) for silicate flotation Depressant: Phosphoric acid for phosphate mineral depression Applicable Ores: Calcareous phosphate ores (phosphate-dolomite/calcite associations) 2.3.3 Double Reverse Flotation A two-stage process: ①Primary flotation of carbonates; ②Secondary flotation of silicates Applicability: Siliceous-calcareous phosphate ores (e.g., Yunnan/Guizhou deposits in China) Advantages: Capable of processing low-grade ores (P₂O₅

Under surface weathering conditions, primary sulfide minerals undergo oxidation reactions with atmospheric oxygen and aqueous solutions, forming secondary oxidized mineral zones. These oxidation zones typically develop in the shallow portions of ore deposits, with their thickness controlled by regional geological conditions, ranging between 10-50 meters.   Based on the oxidation degree of metallic elements in the ore (i.e., the percentage of oxidized minerals relative to total metal content), ores can be classified into three categories: Oxidized ore: oxidation rate >30% Sulfide ore: oxidation rate 10 (leads to PbS film detachment) Process optimizations: ✓ Partial NaHS substitution for Na₂S ✓ pH adjustment with (NH₄)₂SO₄ (1-2 kg/t) or H₂SO₄ ✓ Staged reagent addition (test-determined)   1.2. Zinc Oxide Minerals and Flotation Methods 1.2.1. Principal Industrial Zinc Oxide Minerals Mineral Chemical Formula Zinc Content Density (g/cm³) Hardness Smithsonite ZnCO₃ 52% 4.3 5 Hemimorphite H₂Zn₂SiO₅ 54% 3.3–3.6 4.5–5.0 1.2.2 Flotation Process Options 1.2.2.1. Hot Sulfidization Flotation Key Parameters: Pulp Temperature: 60–70°C (critical for ZnS film formation) Activator: CuSO₄ (0.2–0.5 kg/t) Collector: Xanthates (e.g., potassium amyl xanthate) Applicability: Effective for smithsonite Limited efficiency for hemimorphite 1.2.2.2. Fatty Amine Flotation Process Control: pH Adjustment: 10.5–11 (using Na₂S) Collector: Primary fatty amines (e.g., dodecylamine acetate) Slime Management: Option A: Pre-flotation desliming Option B: Dispersants (sodium hexametaphosphate + Na₂SiO₃) Innovative Approach: Amine-Na₂S emulsion (1:50 ratio) Eliminates need for desliming   1.3. Beneficiation Processes for Mixed Lead-Zinc Ores 1.3.1. Process Flow Options 1.3.1.1. Sulfides-First, Oxides-Later Circuit Sequence: Sulfide minerals (bulk/selective flotation) → Oxidized lead → Oxidized zinc Advantages: Maximizes sulfide recovery before oxide treatment Reduces reagent interference between mineral types 1.3.1.2. Lead-First, Zinc-Later Circuit Sequence: Lead sulfides → Lead oxides → Zinc sulfides → Zinc oxides Advantages: Ideal for ores with clear Pb/Zn liberation boundaries Enables tailored reagent schemes for each metal 1.3.2. Process Optimization Guidelines Highly oxidized ores (ZnO >30%): Use amine collectors to co-recover: Oxidized zinc minerals Residual zinc sulfides Typical dosage: 150–300 g/t C12–C18 amines Process selection criteria: Requires: Ore characterization studies (MLA/QEMSCAN) Bench-scale testing (including locked-cycle tests) Decision factors: Oxidation ratio (PbO/ZnO vs. PbS/ZnS) Mineralogical complexity index     2. Flotation Characteristics of Multivalent Metal Salt Minerals 2.1. Representative Minerals Phosphates: Apatite [Ca₅(PO₄)₃(F,Cl,OH)] Tungstates: Scheelite (CaWO₄) Fluorides: Fluorite (CaF₂) Sulfates: Barite (BaSO₄) Carbonates: Magnesite (MgCO₃) Siderite (FeCO₃) 2.2. Key Flotation Properties Characteristic Description Crystal Structure Dominant ionic bonding Surface Properties Strong hydrophilicity (contact angle