Method for strengthening separation of micro-fine particle tungsten ore and calcium-containing minerals based on metal ions

Abstract

The invention discloses a method for strengthening separation of micro-fine particle tungsten ore and calcium-containing minerals based on metal ions, and relates to the technical field of mineral separation, and the method comprises the following specific steps: step 1, weighing a plurality of mixed ore samples of scheelite and calcium-containing minerals, and adding the mixed ore samples into a flotation tank for stirring; 2, adding a pH regulator to regulate the pH value of the ore pulp; 3, preparing a metal-organic / inorganic complex inhibitor; 4, adding a metal-organic / inorganic acid complex inhibitor to adjust the ore pulp; 5, an active agent is added to adjust the ore pulp; 6, a collecting agent solution is added to adjust the hydrophobicity of the surface of the mineral; and 7, adding a foaming agent to adjust the ore pulp. According to the method, selective separation of scheelite and calcium-containing minerals is enhanced by adopting the metal-organic / inorganic acid complex inhibitor, and the grade and the recovery rate of WO3 in concentrate are improved; meanwhile, the method is environmentally friendly, remarkable in environmental benefit and economic benefit and suitable for industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of mineral separation, in particular to a method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions. Background Art

[0002] Mineral separation is a method of separating minerals into different parts or purifying certain minerals by using machinery, instruments or reagents according to the differences in their physical and chemical properties. The main separation methods are: magnetic separation based on the difference in mineral magnetic properties; gravity separation, water washing, blowing, heavy liquid separation, magnetic gravity separation, and heavy melt separation based on the density of minerals; electrostatic separation, electrochemical separation, and dielectric separation based on the electrical properties of minerals; flotation separation based on the floatability of minerals; and selective chemical dissolution and membrane reaction separation based on the chemical properties of minerals.

[0003] Tungsten is a widely distributed element, which is almost universally found in all kinds of rocks, but the content is low. It can only be enriched by relevant geological processes to form deposits and be mined as commercial ore. The average content of tungsten in the earth's crust is 1.3×10 -6 , the average content in granite is 1.5×10 -6 Tungsten is mainly present as a hexavalent cation in nature, with an ionic radius of 0.68×10 - 10 m; due to W 6+ The ion radius is small, the charge is high, it has strong polarization ability, and it is easy to form complex anions. Therefore, tungsten is mainly in the form of complex anions [WO4] 2- , and Fe in solution 2+ , Mn 2+ , Ca 2+ The cations combine to form wolframite or scheelite precipitation; the crystallization temperature of wolframite is 320-240℃, and the crystallization temperature of scheelite is 300-200℃; in the surface process, since tungsten-containing minerals are relatively stable, placer mines are often formed; but under acidic conditions, tungsten-containing minerals can be decomposed and dissolved in surface water in the form of WO3, forming certain secondary minerals of tungsten under certain conditions; sometimes they are adsorbed by clay or iron-manganese oxides in the form of mineral particles or ions and accumulated in shale, mudstone fine sandstone and iron-manganese ore layers; nowadays, strata-bound tungsten deposits and tungsten ore source layers have been found in ancient metamorphic rock systems, indicating that tungsten can also be enriched to a certain extent during metamorphism.

[0004] The important minerals of tungsten are tungstates; in the process of mineralization, they can react with [WO4] 2- There are only a few cations bound to complex anions, mainly Ca 2+ , Fe 2+ , Mn 2+ , Pb 2+ , followed by Cu2+ 、Zn 2+ 、Al 3+ , Fe3+, Y3+, etc., so the types of minerals are limited. Now only more than 20 kinds of tungsten minerals and tungsten-containing minerals have been found in the earth's crust, namely, wolframite family: wolframite, wolframite, wolframite; scheelite family: scheelite, molybdenum scheelite, copper scheelite; tungsten schist minerals: tungsten schist, hydrotungsten schist, high-iron tungsten schist, yttrium tungsten schist, copper tungsten schist, hydrotungsten aluminum schist; uncommon tungsten minerals: wolframite, clinopyroclastic tungsten, molybdenum tungsten, wolframite, bismuth tungsten, antimony tungsten pyrochlore, titanium yttrium thorite, tungsten sulfide, etc.

[0005] Although more than 20 kinds of tungsten minerals and tungsten-containing minerals have been discovered, only wolframite and scheelite have economic value for mining; wolframite (Fe, Mn) WO4 contains WO376%; scheelite CaWO4 contains WO380.6%.

[0006] Scheelite and calcium-containing minerals have the same localizing ions on their surfaces, similar physical and chemical properties, and similar adsorption behaviors on collectors, making the flotation separation of scheelite and calcium-containing gangue minerals a global problem. Mineral processing workers have done a lot of work on the selective separation of scheelite and calcium-containing gangue minerals, especially in the types, adsorption mechanisms, theoretical calculations, and applications of the two most important types of drugs in the flotation process of tungsten ore - collectors (anionic collectors, cationic collectors, and combined collectors, etc.) and inhibitors (organic inhibitors and inorganic inhibitors). These research works have greatly promoted people's understanding of the flotation process of tungsten minerals and the development of surface physical chemistry.

[0007] The essential reason for the difficulty in flotation separation of scheelite and calcium-containing minerals is that the solubility of the mineral surface is relatively large. The dissolved components of the mineral will react chemically on the surface of another mineral, resulting in similar chemical composition, electrical properties and floatability of the mineral surface. Therefore, the essence of flotation separation between tungsten ore and calcium-containing minerals is still a selectivity problem. Metal ions play an important role in the flotation process of minerals, especially the activation flotation effect. Recent studies have found that metal-organic / inorganic complexes formed by metal ions and flotation agents also play an important role in the flotation process of oxide ores, and have certain advantages in terms of capture capacity and selectivity. Using the "principle of metal ion coordination to regulate molecular assembly" to design new materials and agents with special properties has become a hot topic in international research. However, research on metal-organic / inorganic complexes in the field of flotation is still in its infancy. Therefore, the use of metal ions to simultaneously form metal-organic / inorganic complex inhibitors with organic and inorganic inhibitors to enhance the inhibitory effect on calcite has important application prospects in the flotation separation of scheelite and calcite. Summary of the invention

[0008] In view of the deficiencies in the prior art, the present invention provides a method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions, which solves the problems raised in the above-mentioned background technology.

[0009] To achieve the above purpose, the present invention is implemented by the following technical scheme: A method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions, comprising the following specific steps:

[0010] Step 1: Weigh a number of mixed samples of scheelite and calcium-containing minerals, add them into the flotation tank and stir;

[0011] Step 2: Adding a pH adjuster to adjust the pH value of the slurry;

[0012] Step 3: preparing metal-organic / inorganic complex inhibitors;

[0013] Step 4: Add metal-organic / inorganic acid complex inhibitor to adjust the slurry;

[0014] Step 5: Add active agent to adjust the slurry;

[0015] Step 6: Add collector solution to adjust the hydrophobicity of the mineral surface;

[0016] Step 7: Add a frother to adjust the slurry;

[0017] Step 8: Perform flotation and scraping.

[0018] Step 9: Dry and weigh the foam product, test the grade of WO3, and calculate the recovery rate of WO3.

[0019] Optionally, the calcium-containing mineral in step one is one or more of fluorite and calcite, and the mineral particle size is less than 0.038 μm.

[0020] Optionally, the pH adjuster in step 2 is one of hydrochloric acid, sulfuric acid, sodium carbonate and sodium hydroxide, and its pH value is 2.0 to 12.0.

[0021] Optionally, the preparation of the metal-organic / inorganic acid complex inhibitor in step 3 is carried out using Pb 2+ , Cu 2+ 、N i 2+ , Er 3+ 、A l 3+ , Fe 3+ ,La 3+ 、Zn 2+ One of the chloride, nitrate or sulfate solutions is reacted with the organic inhibitor and the inorganic inhibitor solution in a proportion in an environment with a pH value of 1 to 12 and a temperature of 0 to 100° C. for 0.05 to 120 hours;

[0022] in,

[0023] The organic inhibitor is one of succinic acid, quinic acid, epoxysuccinic acid, tannic acid, pyrogallic acid, salicylic acid, gallic acid, sodium carboxymethyl cellulose, humic acid, etc.;

[0024] The inorganic inhibitor is one of sodium silicate, sodium hexametaphosphate, sodium fluorosilicate, etc.;

[0025] The ratio of metal ions to inhibitors is 0.1-10:1, wherein the ratio of organic inhibitors to inorganic inhibitors is 0.5-10:0.5-10.

[0026] Optionally, in step 4, the dosage of the metal-organic / inorganic acid complex inhibitor is 1 mg / L to 200 mg / L.

[0027] Optionally, the activator in step five is lead nitrate, and the amount of the activator is 0 to 800 mg / L.

[0028] Optionally, the type and specific dosage of the collector in step 6 are as follows:

[0029] Sodium oleate, dosage: 50-300 mg / L;

[0030] Benzohydroxamic acid, dosage: 10-100 mg / L;

[0031] Salicylic hydroxamic acid, dosage: 10-100 mg / L;

[0032] Sodium oleate + benzohydroxamic acid, dosage: 40-300 mg / L; ratio: sodium oleate 10%-90%, benzohydroxamic acid 10%-90%;

[0033] Sodium oleate + salicylic acid, dosage: 20-200 mg / L; ratio: sodium oleate 20%-90%, salicylic acid 10%-80%.

[0034] Optionally, the foaming agent in step seven is one of pine oil, methyl isobutyl carbinol (MIBC), and BK201, and the amount of the foaming agent is 0 to 50 mg / L.

[0035] Optionally, the flotation scraping time in step eight is 0 to 10 minutes.

[0036] The present invention provides a method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions, which has the following beneficial effects:

[0037] The metal ion-based enhanced separation method of fine-grained scheelite and calcium-containing minerals uses a metal-organic / inorganic acid complex inhibitor to enhance the selective separation of scheelite and calcium-containing minerals, thereby improving the grade and recovery rate of WO3 in the concentrate; the metal-organic / inorganic acid complex inhibitor is formed by metal ions and organic inhibitors and inorganic inhibitors, with a simple process and low cost; at the same time, the process method is green and environmentally friendly, with significant environmental and economic benefits, and is suitable for industrial production. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0039] Example 1: A method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions, comprising the following specific steps:

[0040] Step 1: Weigh a number of mixed ore samples of scheelite and calcium-containing minerals, add them into a flotation tank for stirring, and the calcium-containing mineral is fluorite, and its mineral particle size is less than 0.038 μm;

[0041] Step 2: adding sodium carbonate to adjust the pH value of the slurry to 9.0;

[0042] Step 3: preparing metal-organic / inorganic complex inhibitors;

[0043] Preparation of metal-organic / inorganic acid complex inhibitors using Al 3+ , the sulfate solution and the organic inhibitor solution were reacted in proportion in an environment with a pH value of 4.5 and a temperature of 75.0°C for 1.2 hours;

[0044] in,

[0045] The organic inhibitor used was succinic acid;

[0046] The inorganic inhibitor is sodium hexametaphosphate;

[0047] The ratio of metal ions to inhibitors is 1:2.3, of which the ratio of organic inhibitors to inorganic inhibitors is 2:1;

[0048] Step 4: Add metal-organic / inorganic acid complex inhibitor to adjust the slurry, the amount of metal-organic / inorganic acid complex inhibitor is 25 mg / L;

[0049] Step 5: Add lead nitrate to adjust the slurry, the amount of lead nitrate is: 30mg / L;

[0050] Step 6: Add sodium oleate solution to adjust the hydrophobicity of the mineral surface, the amount of sodium oleate is 45 mg / L;

[0051] Step 7: Add pine oil to adjust the slurry, the amount of pine oil is 14 mg / L;

[0052] Step 8: Carry out flotation scraping, the flotation scraping time is 5 minutes.

[0053] Step 9: Dry and weigh the foam product, test the grade of WO3, and calculate the recovery rate of WO3.

[0054] Table 1 Separation of scheelite and calcite

[0055]

[0056] Example 2: A method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions, comprising the following specific steps:

[0057] Step 1: Weigh a number of mixed ore samples of scheelite and calcium-containing minerals, add them into a flotation tank for stirring, and the calcium-containing mineral is calcite, and its mineral particle size is less than 0.019 μm;

[0058] Step 2: adding sodium hydroxide to adjust the pH value of the slurry, wherein the pH value of the sodium hydroxide is 8.6;

[0059] Step 3: preparing metal-organic / inorganic complex inhibitors;

[0060] Preparation of metal-organic / inorganic acid complex inhibitors using Fe 3+ React with organic inhibitor solution in proportion in an environment with a pH value of 4.0 and a temperature of 40.0°C for 2.0h;

[0061] in,

[0062] Tannic acid was used as the organic inhibitor;

[0063] The inorganic inhibitor is sodium silicate;

[0064] The ratio of metal ions to inhibitors is 1:3, of which the ratio of organic inhibitors to inorganic inhibitors is 3:2;

[0065] Step 4: Add metal-organic / inorganic acid complex inhibitor to adjust the slurry, the amount of metal-organic / inorganic acid complex inhibitor is 110 mg / L;

[0066] Step 5: Add lead nitrate to adjust the slurry, the amount of lead nitrate is: 25mg / L;

[0067] Step 6: Add benzohydroxamic acid to adjust the hydrophobicity of the mineral surface, the amount of benzohydroxamic acid used is 25 mg / L;

[0068] Step 7: adding methyl isobutyl carbinol (MI BC) to adjust the slurry, the dosage of methyl isobutyl carbinol (MIBC) is 10 mg / L;

[0069] Step 8: Carry out flotation scraping, the flotation scraping time is 3 minutes.

[0070] Step 9: Dry and weigh the foam product, test the grade of WO3, and calculate the recovery rate of WO3.

[0071] Table 2 Separation of scheelite and calcite

[0072]

[0073] Example 3: A method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions, comprising the following specific steps:

[0074] Step 1: Weigh a number of mixed ore samples of scheelite and calcium-containing minerals, add them into a flotation tank for stirring, and the calcium-containing mineral is calcite, and its mineral particle size is less than 0.038 μm;

[0075] Step 2: adding sodium hydroxide to adjust the pH value of the slurry to 8.2;

[0076] Step 3: preparing metal-organic / inorganic complex inhibitors;

[0077] Preparation of metal-organic / inorganic acid complex inhibitors using Fe 3+ React with organic inhibitor solution in proportion at pH 3.9 and 82.3°C for 4.5h;

[0078] in,

[0079] The organic inhibitor is sodium carboxymethyl cellulose;

[0080] The inorganic inhibitor is sodium fluorosilicate;

[0081] The ratio of metal ions to inhibitors is 1:3.5, of which the ratio of organic inhibitors to inorganic inhibitors is 2:1.5;

[0082] Step 4: Add metal-organic / inorganic acid complex inhibitor to adjust the slurry, the amount of metal-organic / inorganic acid complex inhibitor is 156 mg / L;

[0083] Step 5: Add lead nitrate to adjust the slurry, the amount of lead nitrate is: 20mg / L;

[0084] Step 6: Add sodium oleate + benzohydroxamic acid solution to adjust the hydrophobicity of the mineral surface, the amount of sodium oleate + benzohydroxamic acid is 30 mg / L; the ratio is: sodium oleate 48.3%, benzohydroxamic acid 51.7%;

[0085] Step 7: Add BK201 to adjust the slurry, the dosage of BK201 is 20 mg / L;

[0086] Step 8: Carry out flotation scraping, the flotation scraping time is 3 minutes.

[0087] Step 9: Dry and weigh the foam product, test the grade of WO3, and calculate the recovery rate of WO3.

[0088] Table 3 The data in the table of separation of scheelite and calcite do not correspond to the implementation case

[0089]

[0090] Conclusion: As shown in the calculation results of Tables 1 to 3, the use of metal-organic / inorganic acid complex inhibitors strengthens the selective separation of scheelite and calcium-containing minerals, and improves the grade and recovery rate of WO3 in the concentrate; the use of metal ions and organic inhibitors and inorganic inhibitors to form metal-organic / inorganic acid complex inhibitors has a simple process and low cost; at the same time, the process method is green and environmentally friendly, with significant environmental and economic benefits, and is suitable for industrial production.

[0091] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions, characterized in that: The specific steps include: Step 1: Weigh a number of mixed samples of scheelite and calcium-containing minerals, add them into the flotation tank and stir; Step 2: Adding a pH adjuster to adjust the pH value of the slurry; Step 3: preparing metal-organic / inorganic complex inhibitors; Step 4: Add metal-organic / inorganic acid complex inhibitor to adjust the slurry; Step 5: Add active agent to adjust the slurry; Step 6: Add collector solution to adjust the hydrophobicity of the mineral surface; Step 7: Add a frother to adjust the slurry; Step 8: Perform flotation and scraping. Step 9: Dry and weigh the foam product, test the grade of WO3, and calculate the recovery rate of WO3.

2. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: The calcium-containing mineral in step 1 is one or more of fluorite and calcite, and the mineral particle size is less than 0.038 μm.

3. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: The pH adjuster in step 2 is one of hydrochloric acid, sulfuric acid, sodium carbonate and sodium hydroxide, and its pH value is 2.0-12.

0.

4. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: The preparation of the metal-organic / inorganic acid complex inhibitor in step 3 is carried out by using Pb 2+ , Cu 2+ 、Ni 2+ , Er 3+ 、Al 3+ , Fe 3+ ,La 3+ 、Zn 2+ One of the chloride, nitrate or sulfate solutions is reacted with the organic inhibitor and the inorganic inhibitor solution in a proportion in an environment with a pH value of 1 to 12 and a temperature of 0 to 100° C. for 0.05 to 120 hours; in, The organic inhibitor is one of succinic acid, quinic acid, epoxysuccinic acid, tannic acid, pyrogallic acid, salicylic acid, gallic acid, sodium carboxymethyl cellulose, and humic acid; The inorganic inhibitor is one of sodium silicate, sodium hexametaphosphate and sodium fluorosilicate; The ratio of metal ions to inhibitors is 0.1-10:1, wherein the ratio of organic inhibitors to inorganic inhibitors is 0.5-10:0.5-10.

5. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: In the step 4, the dosage of the metal-organic / inorganic acid complex inhibitor is 1 mg / L to 200 mg / L.

6. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: The activator in step 5 is lead nitrate, and the amount of the activator is 0-800 mg / L.

7. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: The type and specific dosage of the collector in step 6 are as follows: Sodium oleate, dosage: 50-300 mg / L; Benzohydroxamic acid, dosage: 10-100 mg / L; Salicylic hydroxamic acid, dosage: 10-100 mg / L; Sodium oleate + benzohydroxamic acid, dosage: 40-300 mg / L; ratio: sodium oleate 10%-90%, benzohydroxamic acid 10%-90%; Sodium oleate + salicylic acid, dosage: 20-200 mg / L; ratio: sodium oleate 20%-90%, salicylic acid 10%-80%.

8. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: The foaming agent in step seven is one of pine oil, methyl isobutyl carbinol and BK201, and the dosage of the foaming agent is 0-50 mg / L.

9. The method for separating fine-grained tungsten ore from calcium-containing minerals based on metal ions according to claim 1, characterized in that: The flotation scraping time in step eight is 0 to 10 minutes.

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