Method for separating and extracting valuable metal titanium from vanadium-containing mineral

Abstract

The invention relates to the technical field of mineral separation, and discloses a method for separating and extracting valuable metal titanium from vanadium-containing minerals, which comprises the following steps: S1, crushing and grading the vanadium-containing minerals to obtain mineral powder; s2, activating the mineral powder to obtain mineral powder; s3, an inhibitor and a catching agent are added into the mineral powder for roughing, and a titanium-rich phase 1 and a lean phase 1 are obtained; and S4, the titanium-rich phase 1 is subjected to concentration and water adding to form flotation pulp, an inhibitor and a collecting agent are added into the flotation pulp, concentration is conducted again, and a titanium-rich phase 2 and a titanium-poor phase 2 are obtained. According to the method provided by the invention, the vanadium-containing minerals are subjected to activation pretreatment, the adhesion effect of the collecting agent on the surface of the titanium-containing phase can be improved, and the recovery rate of titanium dioxide can be greater than 70% by adopting the inhibitors carboxymethyl cellulose and cytidine and the collecting agents diethyl phenylphosphonate and 3-chloro-o-anisidine.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing, in particular to a method for separating and extracting valuable metal titanium from vanadium-containing minerals. Background Art

[0002] Vanadium-containing minerals involve a wide range of raw material sources, mainly including intermediate products or tailings produced in the process of mining, smelting and sorting of vanadium-titanium magnetite, tailings produced by calcification and roasting of vanadium slag, tailings produced in the process of shale vanadium extraction, and other vanadium-containing minerals. Vanadium and titanium often coexist in minerals, so various vanadium-containing minerals contain titanium to varying degrees. Titanium itself is also an important strategic metal element. Extracting titanium from vanadium-containing minerals has important economic significance. The long-term stacking of various tailings will cause environmental pollution, and they cannot be discharged to the outside, which has caused great difficulties in production. The utilization of vanadium-containing minerals can not only realize the recovery of valuable elements and avoid waste of resources, but also save costs and greatly reduce environmental pollution.

[0003] Common methods for extracting titanium can be roughly divided into pyrometallurgy, hydrometallurgy, selective precipitation separation technology, etc. Hydrometallurgy mainly uses sulfuric acid, hydrochloric acid, mixed acid, etc. to acid-leach and decompose the slag to increase the titanium-rich rate in the filtrate. The residue obtained can be used for the comprehensive utilization of cement. The main problem is that the amount of acid used is large, which seriously corrodes the equipment, and the waste acid produced is easy to cause secondary pollution to the surrounding environment, and the waste liquid after use is extremely difficult to handle. For pyrometallurgy, the principle of thermal reduction is used, and a certain degree of reduction reaction is carried out at high temperature. The operation is simple, and the final product can be used for cement materials, but it destroys the enrichment of titanium, and the subsequent impurity separation operation is complicated, the cost is high, and it is difficult to produce and use. Selective precipitation separation technology is mainly reflected in the enrichment of titanium. The key is to select an optimized titanium-enriched phase, so it is necessary to add appropriate additives to change the composition of the slag containing titanium dioxide. This process has the advantages of short and simple process, low environmental pollution, and the tailings produced can be used as building materials, etc. However, the recovery rate of this process is low, and the grains of the enriched phase are difficult to grow, and the energy consumption is also high.

[0004] At present, the main methods for recovering titanium and iron from vanadium-containing minerals are blast furnace method or pre-reduction-melting method, that is, vanadium slag is pelletized and pre-reduced, and then separated from titanium and iron by electric furnace smelting. Since vanadium slag contains a large amount of alkali metals, the pellets are severely pulverized during the pre-reduction process, which seriously deteriorates the permeability of the material during subsequent smelting and increases smelting energy consumption. In addition, the titanium in the titanium-containing slag after smelting mostly exists in the form of pyroxene phase, perovskite, etc., which is difficult to recycle economically. The oxidized pellets of vanadium slag are severely swollen and pulverized due to reduction, and cannot be used for blast furnace ironmaking. As a result, the titanium resource recovery rate in domestic vanadium slag is generally less than 60%. Foreign vanadium slag is mainly in a dumped state, which not only causes serious waste of resources, but also brings secondary pollution to the environment. Under the background of "dual carbon" in my country, the blast furnace method or the pre-reduction-smelting method both have problems such as high energy consumption and high CO2 emissions. For example, the smelting temperature of domestic electric furnace ironmaking is generally 1500-1800℃, the energy consumption of the blast furnace process is about 300-500kgce / t, and the electricity consumption of the electric furnace smelting process is about 300-350kWh / t.

[0005] The patent CN113234935A discloses a method for extracting vanadium, titanium and chromium from vanadium slag. The method selectively reduces pyroxene and fayalite wrapped outside spinel through low-temperature hydrogen reduction-iron removal by ferric chloride-low-temperature oxalic acid leaching of vanadium slag, destroys its structure, realizes the dissociation of spinel phase and silicate phase, fully exposes the spinel phase, and directly leaches vanadium slag at low temperature by using the acidity and strong complexing property of oxalic acid, destroys the spinel structure, and makes vanadium, titanium and chromium complex with oxalate into solution, thereby realizing the co-extraction of vanadium, titanium and chromium. The present invention extracts vanadium, titanium and chromium from vanadium slag, and the leaching rate is greater than 99%; however, the method not only increases energy consumption and produces waste acid, but also has a long process flow.

[0006] Patent CN117737330A discloses a method for recovering iron and titanium from vanadium-extracting slag by hydrogen-based reduction-magnetic separation, comprising: preparing raw balls from the sodium-extracting vanadium-extracting slag through fine grinding, acid leaching, concentration, filtration and high-pressure roller grinding; directly reducing the raw balls through oxidative roasting and a hydrogen-based vertical furnace containing a heating device combined with heat pipe heat exchange and electromagnetic induction to obtain reduced balls containing elemental iron and titanium oxide; and crushing, ball milling, fine grinding and magnetic separation of the reduced balls to obtain reduced iron powder and high-titanium slag. This method uses a high-temperature process and has excessively high energy consumption costs.

[0007] Patent CN111041200A discloses a method for leaching vanadium, titanium and chromium from vanadium, titanium and chromium raw materials by hydrothermal organic acid. The method is to directly leach vanadium slag with high concentration oxalic acid under high temperature and high pressure conditions to achieve the co-extraction of vanadium, titanium and chromium, and solve the "three wastes" problem. However, the method needs to be carried out under high temperature, high pressure and high acidity conditions, and has high requirements for equipment.

[0008] In order to effectively recover titanium and iron resources from vanadium slag, it is urgent to develop an economical, low-energy, and environmentally friendly method for separating titanium and iron. As a conventional mineral processing method, flotation has a large processing capacity and a short process flow, and its position in mineral separation is becoming increasingly important. Existing studies have focused on the flotation of high-grade titanium-containing minerals or titanium slag, but there are few studies on the flotation separation of titanium in vanadium-containing minerals. Summary of the invention

[0009] Technical Problems Solved by the Invention

[0010] To develop a flotation separation method suitable for titanium in vanadium-containing minerals.

[0011] Technical solution adopted by the present invention

[0012] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0013] S1. Crushing and classifying vanadium-containing minerals to obtain mineral powders;

[0014] S2 mineral powder is activated to obtain mineral powder;

[0015] S3 adds inhibitors and scavengers to the ore powder for rough separation to obtain titanium-rich phase 1 and lean phase 1;

[0016] S4 titanium-rich phase 1 is concentrated and water is added to form a flotation pulp, and an inhibitor and a collector are added to the flotation pulp, and then concentrated to obtain titanium-rich phase 2 and titanium-poor phase 2. The number of flotation can be selected multiple times according to actual conditions.

[0017] According to some preferred embodiments, in S1, the vanadium-containing mineral includes at least one of the intermediate products or tailings produced in the mining, smelting and sorting process of vanadium-titanium magnetite, the tailings produced by calcification and roasting of vanadium slag to extract vanadium, the tailings produced in the process of shale vanadium extraction, and other vanadium-containing minerals.

[0018] According to some preferred embodiments, in S1, the vanadium-containing mineral is crushed and classified to a particle size range of 1 to 74 μm.

[0019] According to some preferred embodiments, in S2, the activator includes at least one of sulfuric acid, sulfurous acid, sodium sulfide, copper sulfate, oxalic acid, lime, sulfur dioxide, lead nitrate, sodium carbonate, sodium hydroxide, lead acetate, and barium nitrate; and the concentration of the activator is 0.5 to 1.5 mol / L.

[0020] According to some more preferred embodiments, in S2, the activator includes at least one of oxalic acid, barium nitrate, and lead acetate.

[0021] According to some preferred embodiments, in S2, the activation time is 1 to 3 hours, the temperature is 40 to 80° C., and the solid-liquid ratio is 1:8 to 1:15.

[0022] According to some preferred embodiments, in S3 and S4, the pH value of the roughing and concentrating pulp is 1-6; the time of roughing and concentrating flotation is 5-60 min; the vanadium mineral content of the roughing and concentrating flotation pulp is 10-50wt%.

[0023] According to some preferred embodiments, in S3 and S4, the mass ratio of the inhibitor to the collector is 1-1:1-4.

[0024] According to some preferred embodiments, in S3 and S4, the inhibitor includes carboxymethyl cellulose and cytosine nucleoside, and the ratio of the agents is 1:2 to 1:4; the amount of the inhibitor added is 500 to 2000 g / t, and the stirring time is 3 to 5 min.

[0025] According to some preferred embodiments, in S3 and S4, the capture agent includes diethyl phenylphosphonate and 3-chloro-o-anisidine, and the agent ratio is 1:1 to 1:3; the addition amount of the capture agent is 1000 to 2000 g / t, and the stirring time is 3 to 5 min.

[0026] Beneficial effects achieved by the present invention

[0027] In the method provided by the present invention, the vanadium-containing mineral is activated and pretreated to improve the adhesion effect of the collector on the surface of the titanium-containing phase. The inhibitor carboxymethyl cellulose and cytosine nucleoside and the collector diethyl phenylphosphonate and 3-chloro-o-anisidine are used to make the titanium dioxide recovery rate greater than 70%.

[0028] In the method provided by the present invention: First, the oxygen atom in the phosphonic acid group of diethyl phenylphosphonate can form a four-membered chelate ring or an insoluble compound with the unsaturated lattice cations on the surface of ilmenite. Diethyl phenylphosphonate can chemically interact with the Fe and Ti sites on the surface of ilmenite to form a hydrophobic organic phosphonate at the solid-liquid interface. Second, the amine group in 3-chloro-o-anisidine is hydrolyzed in water to form -NH3 + This positively charged group adsorbs on the surface of ilmenite. The hydrocarbon part has strong hydrophobicity, making the mineral surface hydrophobic. +The group can effectively capture metal oxide minerals. 3-chloro-o-anisidine has strong semi-micelle adsorption on the surface of ilmenite, further forming adsorption groups of minerals and collector molecules, and is less affected by temperature when used. Third, the adsorption of carboxymethyl cellulose on the silicate surface is achieved through the combined action of hydrogen bonds and chemical adsorption. The former is the result of the action of hydroxyl groups in the carboxymethyl cellulose structure and hydroxyl groups in the silicate structure, and the latter is caused by the action of the carboxyl groups of carboxymethyl cellulose and metal ions on the surface of silicates. The amine group and the five-membered ring in cytosine nucleoside can undergo electrostatic adsorption and chemical adsorption with metal ions in the ore. Carboxymethyl cellulose and cytosine nucleoside will adsorb to the silicate phase in vanadium-containing minerals, inhibiting their floating, and occupying the active sites of the silicate phase, preventing the adsorption of collectors on their surface, thereby enhancing the flotation effect.

[0029] The flotation reagent used in the present invention can expand the floatability difference between the titanium-containing phase and other phases and is environmentally friendly.

[0030] The purity of the titanium-containing TiO2 obtained by the method of the present invention can reach 30% or more, so that the titanium resources are effectively recovered. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a schematic diagram of the process of the present invention. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0033] Example 1

[0034] The ore sample is the tailings from vanadium slag after calcification roasting and sulfuric acid leaching to extract vanadium, and its grade is: TiO2=8.67%.

[0035] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0036] S1 The tailings after calcification roasting and vanadium extraction are ball milled with a ball mill, and powder with a particle size of less than 30 microns is selected as the raw material.

[0037] S2: Add 1 mol / L barium nitrate solution to the powder obtained in step S1, with a solid-liquid ratio of 1:10, a heating temperature of 70°C, and an activation time of 2h.

[0038] S3: adding water to the activated sample in step S2 to prepare a slurry, so that the activated slag accounts for 10 wt % in the slurry.

[0039] S4: Add 1000g inhibitor per ton of flotation raw material. Add inhibitors carboxymethyl cellulose and cytosine nucleoside into the flotation tank in a mass ratio of 1:2, and allow them to react with the flotation slurry for 3 minutes.

[0040] S5: Add 2000g collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine into the flotation tank in a mass ratio of 1:1. Stir for 1 minute and adjust the pH value of the slurry to 5. Allow it to act with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape the foam for 10 minutes for a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0041] S6 uses the titanium-rich phase 1# prepared in step S5 as a raw material, maintains the slurry pH value at 5, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and concentrating the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0042] The purity of the titanium-rich phase 2#TiO2 obtained in this example is 32.2%, and the recovery rate is 72.1%.

[0043] Example 2

[0044] The ore sample is the tailings from vanadium slag after sodium roasting and sulfuric acid leaching to extract vanadium, and its grade is: TiO2=9.46%.

[0045] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0046] S1 The tailings after calcification roasting and vanadium extraction are ball milled by a ball mill, and powder with a particle size less than 60 microns is selected as raw material.

[0047] S2: Add the powder obtained in step S1 into 1 mol / L lead acetate solution, with a solid-liquid ratio of 1:8, a heating temperature of 65°C, and an activation time of 3 h.

[0048] S3: adding water to the activated sample in step S2 to prepare a slurry, so that the activated slag accounts for 20 wt % of the slurry.

[0049] S4: Add 1000g inhibitor per ton of flotation raw material. Add inhibitors carboxymethyl cellulose and cytosine nucleoside into the flotation tank in a mass ratio of 1:3, and allow them to react with the flotation pulp for 5 minutes.

[0050] S5: Add 1000g collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine into the flotation tank in a mass ratio of 1:2, stir for 1 minute, adjust the pH value of the slurry to 5; and allow it to act with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase, then aerate for 1 minute and scrape the foam for 10 minutes for a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0051] S6 uses the titanium-rich phase 1# prepared in step S5 as a raw material, maintains the slurry pH value at 5, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and concentrating the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0052] S7 repeats the same concentrating process twice for the titanium-rich phase 2# after the first concentrating to obtain the final high-titanium grade material.

[0053] The purity of the titanium-rich phase 2#TiO2 obtained in this example is 36.23%, and the recovery rate is 73.19%.

[0054] Example 3

[0055] The ore sample is vanadium slag from smelting of vanadium-titanium magnetite in a blast furnace, and its grade is: TiO2=5.75%.

[0056] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0057] S1 The tailings after calcification roasting and vanadium extraction are ball milled by a ball mill, and powder with a particle size less than 20 microns is selected as raw material.

[0058] S2: Add 0.5 mol / L of a mixed solution of sodium sulfite and sodium carbonate (mass ratio is 1:1) to the powder obtained in step S1, with a solid-liquid ratio of 1:12, a heating temperature of 55°C, and an activation time of 3h.

[0059] S3: adding water to the sample obtained in step S2 after the activation treatment to prepare a slurry, so that the activated slag accounts for 25 wt % of the slurry.

[0060] S4: Add 1000g inhibitor per ton of flotation raw material. Add inhibitors carboxymethyl cellulose and cytosine nucleoside into the flotation tank in a mass ratio of 1:3, and allow them to react with the flotation pulp for 5 minutes.

[0061] S5: Add 1000g collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine into the flotation tank in a mass ratio of 1:4, stir for 1 minute, adjust the pulp pH to 2; and allow it to act with the flotation pulp for 3 minutes to effectively capture the titanium-containing phase, then aerate for 1 minute and scrape the foam for 30 minutes for a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0062] S6 uses the titanium-rich phase 1# prepared in step S3 as a raw material, maintains the slurry pH value at 2, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and finely selects the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0063] S7 repeats the same concentration process for 3 times on the titanium-rich phase 2# after the first concentration to obtain the final high-titanium grade material.

[0064] The purity of the titanium-rich phase 2#TiO2 obtained in this example is 32.2%, and the recovery rate is 75.15%.

[0065] Example 4

[0066] The ore sample is vanadium slag from smelting of vanadium-titanium magnetite in a blast furnace, and its grade is: TiO2=5.75%.

[0067] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0068] S1 The tailings after calcification roasting and vanadium extraction are ball milled with a ball mill, and powder with a particle size less than 15 microns is selected as the raw material.

[0069] S2: Add 0.5 mol / L of a mixed solution of sodium sulfite and lead nitrate (mass ratio is 2:1) to the powder obtained in step S1, with a solid-liquid ratio of 1:12, a heating temperature of 45°C, and an activation time of 2h.

[0070] S3: adding water to the activated sample of step S2 to prepare a slurry, so that the activated slag accounts for 30wt% of the slurry.

[0071] S4: Add 1500g inhibitor per ton of flotation raw material. Add inhibitors carboxymethyl cellulose and cytosine nucleoside into the flotation tank in a mass ratio of 1:3, and allow them to act on the flotation slurry for 5 minutes.

[0072] S5: Add 1800g collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine into the flotation tank in a mass ratio of 1:4, stir for 1 minute, adjust the pulp pH to 1; and allow it to act with the flotation pulp for 3 minutes to effectively capture the titanium-containing phase, then aerate for 1 minute and scrape the foam for 30 minutes for a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0073] S6 uses the titanium-rich phase 1# prepared in step S3 as a raw material, maintains the slurry pH value at 1, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and concentrating the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0074] S7 repeats the same concentration process for 3 times on the titanium-rich phase 2# after the first concentration to obtain the final high-titanium grade material.

[0075] The purity of the titanium-rich phase 2#TiO2 obtained in this example is 34.28%, and the recovery rate is 74.17%.

[0076] Example 5

[0077] The ore sample is the tailings from stone coal vanadium ore after roasting and acid leaching to extract vanadium, and its grade is: TiO2=6.28%.

[0078] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0079] S1 uses a ball mill to process the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 35 microns as raw material.

[0080] S2: Add the powder obtained in step S1 into a mixed solution of 1.5 mol / L sodium sulfite and barium nitrate (mass ratio is 1:2), the solid-liquid ratio is 1:11, the heating temperature is 65°C, and the activation time is 1.5h.

[0081] S3: adding water to the sample obtained in step S2 after the activation treatment to prepare a slurry, so that the activated slag accounts for 35 wt % of the slurry.

[0082] S4: Add 800g inhibitor per ton of flotation raw material. Add inhibitors carboxymethyl cellulose and cytosine nucleoside into the flotation tank in a mass ratio of 1:4, and allow them to act on the flotation slurry for 5 minutes.

[0083] S5: Add 1400g of collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine into the flotation tank in a mass ratio of 1:1. Stir for 1 minute and adjust the pulp pH to 4. Allow it to react with the flotation pulp for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape the foam for 50 minutes for a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0084] S6 uses the titanium-rich phase 1# prepared in step S3 as a raw material, maintains the slurry pH value at 4, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and finely selects the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0085] S7 repeats the same concentrating process twice for the titanium-rich phase 2# after the first concentrating to obtain the final high-titanium grade material.

[0086] The purity of the titanium-rich phase 2#TiO2 obtained in this example is 36.24%, and the recovery rate is 75.48%.

[0087] Example 6

[0088] The ore sample is the tailings from direct acid leaching of vanadium from stone coal vanadium ore, and its grade is: TiO2=7.44%.

[0089] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0090] S1 The tailings after calcification roasting and vanadium extraction are ball milled with a ball mill, and powder with a particle size less than 15 microns is selected as the raw material.

[0091] S2: Add the powder obtained in step S1 into a 1 mol / L mixed solution of barium nitrate, sodium carbonate and lead acetate (the mass ratio of the three is 1:1:1), the solid-liquid ratio is 1:12, the heating temperature is 50°C, and the activation time is 1.5h.

[0092] S3: adding water to the activated sample of step S2 to prepare a slurry, so that the activated slag accounts for 40wt% of the slurry.

[0093] S4: Add 800g inhibitor per ton of flotation raw material. Add inhibitors carboxymethyl cellulose and cytosine nucleoside into the flotation tank in a mass ratio of 1:3, and allow them to react with the flotation pulp for 4 minutes.

[0094] S5: Add 1500g collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine into the flotation tank in a mass ratio of 1:4. Stir for 1 minute and adjust the pulp pH to 3. Allow it to react with the flotation pulp for 4 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape the foam for 40 minutes for a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0095] S6 uses the titanium-rich phase 1# prepared in step S3 as a raw material, maintains the slurry pH value at 3, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and finely selects the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0096] S7 repeats the same concentrating process twice for the titanium-rich phase 2# after the first concentrating to obtain the final high-titanium grade material.

[0097] The purity of the titanium-rich phase 2#TiO2 obtained in this example is 36.27%, and the recovery rate is 77.65%.

[0098] Comparative Example 1

[0099] The difference between this comparative example and Example 3 is that this comparative example does not undergo the activation treatment of step S2 in Example 3.

[0100] The ore sample is vanadium slag from smelting of vanadium-titanium magnetite in a blast furnace, and its grade is: TiO2=5.75%.

[0101] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0102] S1 The tailings after calcification roasting and vanadium extraction are ball milled by a ball mill, and powder with a particle size less than 20 microns is selected as raw material.

[0103] S2: adding water to the sample treated in step S1 to prepare a slurry, so that the activated slag mass accounts for 25wt% in the slurry.

[0104] S3: Add 1000g inhibitor per ton of flotation raw material. Add inhibitors carboxymethyl cellulose and cytosine nucleoside into the flotation tank in a mass ratio of 1:3, and allow them to act on the flotation slurry for 5 minutes.

[0105] S4: Add 1000g collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine into the flotation tank in a mass ratio of 1:4, stir for 1 minute, adjust the pulp pH to 2; and allow it to act with the flotation pulp for 3 minutes to effectively capture the titanium-containing phase, then aerate for 1 minute and scrape the foam for 30 minutes to perform a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0106] S5 uses the titanium-rich phase 1# prepared in step S3 as a raw material, maintains the slurry pH value at 2, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and finely selects the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0107] S6 repeats the same concentrating process for 3 times on the titanium-rich phase 2# after the first concentrating to obtain the final high-titanium grade material.

[0108] The purity of the titanium-rich phase 2#TiO2 obtained in this comparative example is 25.32%, and the recovery rate is 66.35%.

[0109] Comparative Example 2

[0110] The difference between this comparative example and Example 5 is that the inhibitor in this comparative example is carboxymethyl cellulose and the collector is diethyl phenylphosphonate.

[0111] The ore sample is the tailings from stone coal vanadium ore after roasting and acid leaching to extract vanadium, and its grade is: TiO2=6.28%.

[0112] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0113] S1 uses a ball mill to process the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 35 microns as raw material.

[0114] S2: Add the powder obtained in step S1 into a mixed solution of 1.5 mol / L sodium sulfite and barium nitrate (mass ratio is 1:2), the solid-liquid ratio is 1:11, the heating temperature is 65°C, and the activation time is 1.5h.

[0115] S3: adding water to the sample obtained in step S2 after the activation treatment to prepare a slurry, so that the activated slag accounts for 35 wt % of the slurry.

[0116] S4: Add 800g of inhibitor per ton of flotation raw material. Add the inhibitor carboxymethyl cellulose into the flotation tank and allow it to react with the flotation pulp for 5 minutes.

[0117] S5: Add 1400g of collector per ton of flotation raw material. Add collector diethyl phenylphosphonate into the flotation tank, stir for 1 minute, adjust the pulp pH to 4; and allow it to act with the flotation pulp for 3 minutes to effectively capture the titanium-containing phase, then aerate for 1 minute and scrape the foam for 50 minutes to perform a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0118] S6 uses the titanium-rich phase 1# prepared in step S3 as a raw material, maintains the slurry pH value at 4, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and finely selects the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0119] S7 repeats the same concentrating process twice for the titanium-rich phase 2# after the first concentrating to obtain the final high-titanium grade material.

[0120] The purity of the titanium-rich phase 2#TiO2 obtained in this comparative example is 22.27%, and the recovery rate is 62.36%.

[0121] Comparative Example 3

[0122] The difference between this comparative example and Example 6 is that the inhibitor in this comparative example is cytidine and the collector is 3-chloro-o-anisidine.

[0123] The ore sample is the tailings from direct acid leaching of vanadium from stone coal vanadium ore, and its grade is: TiO2=7.44%.

[0124] A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps:

[0125] S1 The tailings after calcification roasting and vanadium extraction are ball milled with a ball mill, and powder with a particle size less than 15 microns is selected as the raw material.

[0126] S2: Add the powder obtained in step S1 into a 1 mol / L mixed solution of barium nitrate, sodium carbonate and lead acetate (the mass ratio of the three is 1:1:1), the solid-liquid ratio is 1:12, the heating temperature is 50°C, and the activation time is 1.5h.

[0127] S3: adding water to the activated sample of step S2 to prepare a slurry, so that the activated slag accounts for 40wt% of the slurry.

[0128] S4: Add 800g inhibitor per ton of flotation raw material. Add inhibitor cytosine nucleoside into the flotation tank and allow it to react with the flotation slurry for 4 minutes.

[0129] S5: Add 1500g of collector per ton of flotation raw material. Add collector 3-chloro-o-anisidine into the flotation tank, stir for 1 minute, adjust the pulp pH to 3; and allow it to act with the flotation pulp for 4 minutes to effectively capture the titanium-containing phase, then aerate for 1 minute and scrape the foam for 40 minutes to perform a rough selection to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0130] S6 uses the titanium-rich phase 1# prepared in step S3 as a raw material, maintains the slurry pH value at 3, and uses an amount of reagent that is 80% of the amount of reagent used in the roughing step, and finely selects the titanium-rich phase 1# to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0131] S7 repeats the same concentrating process twice for the titanium-rich phase 2# after the first concentrating to obtain the final high-titanium grade material.

[0132] The purity of the titanium-rich phase 2#TiO2 obtained in this comparative example is 26.32%, and the recovery rate is 60.28%.

Claims

1. A method for separating and extracting valuable metal titanium from vanadium-containing minerals, characterized in that: The steps include: S1. Crushing and classifying vanadium-containing minerals to obtain mineral powders; S2 mineral powder is activated to obtain mineral powder; S3 adds inhibitors and scavengers to the ore powder for rough separation to obtain titanium-rich phase 1 and lean phase 1; The S4 titanium-rich phase 1 is concentrated and water is added to form a flotation pulp, and an inhibitor and a collector are added to the flotation pulp, which is then concentrated to obtain a titanium-rich phase 2 and a titanium-poor phase 2.

2. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In S1, the vanadium-containing minerals include at least one of the intermediate products or tailings produced in the process of mining, smelting and sorting of vanadium-titanium magnetite, tailings produced by calcification and roasting of vanadium slag, tailings produced in the process of shale vanadium extraction, and other vanadium-containing minerals.

3. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In S1, the vanadium-containing minerals are crushed and classified, and the particle size ranges from 1 to 74 μm.

4. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In S2, the activator includes at least one of sulfuric acid, sulfurous acid, sodium sulfide, copper sulfate, oxalic acid, lime, sulfur dioxide, lead nitrate, sodium carbonate, sodium hydroxide, lead acetate, and barium nitrate; and the concentration of the activator is 0.5 to 1.5 mol / L.

5. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 4, characterized in that: In S2, the activator includes at least one of oxalic acid, barium nitrate, and lead acetate.

6. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In S2, the activation time is 1 to 3 hours, the temperature is 40 to 80°C, and the solid-liquid ratio is 1:8 to 1:

15.

7. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In S3 and S4, the pH value of the roughing and concentrating pulp is 1-6; the flotation time of the roughing and concentrating is 5-60 minutes; the vanadium mineral content of the roughing and concentrating flotation pulp is 10-50wt%.

8. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In S3 and S4, the mass ratio of the inhibitor to the collector is 1-1:1-4.

9. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to any one of claims 1 to 8, characterized in that: S3 and S4 include at least one of features (1) to (2): (1) The inhibitor includes carboxymethyl cellulose and cytosine nucleoside, and the ratio of the drug is 1:2 to 1:4; (2) The amount of inhibitor added is 500-2000 g / t.

10. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to any one of claims 1 to 8, characterized in that: S3 and S4 include at least one of features (3) to (4): (3) the capture agent includes diethyl phenylphosphonate and 3-chloro-o-anisidine, and the ratio of the agent is 1:1 to 1:3; (4) The amount of scavenger added is 1000-2000 g / t.

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