A method for separating and extracting valuable metal titanium from vanadium-containing minerals

Abstract

The present invention relates to the field of mineral processing technology and discloses a method for separating and extracting valuable metal titanium from vanadium-containing minerals, comprising the following steps: S1 crushing and classifying the vanadium-containing mineral to obtain mineral powder; S2 activating the mineral powder to obtain ore powder; S3 adding an inhibitor and a collector to the ore powder for rough separation to obtain a titanium-rich phase 1 and a depleted phase 1; S4 concentrating the titanium-rich phase 1, adding water to form a flotation pulp, adding an inhibitor and a collector to the flotation pulp, and further concentrating to obtain a titanium-rich phase 2 and a titanium-depleted phase 2. In the method provided by the present invention, the vanadium-containing mineral is pre-treated with activation to improve the adhesion effect of the collector on the surface of the titanium-containing phase. Using inhibitors such as carboxymethyl cellulose and cytosine nucleoside and collectors such as diethyl phenylphosphonate and 3-chloro-o-anisidine can achieve a titanium dioxide recovery rate greater than 70%.

Description

Technical Field

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

[0002] Vanadium-containing minerals come from a wide range of raw materials, primarily including intermediate products or tailings produced during the mining, smelting, and sorting of vanadium-titanium magnetite, tailings from the calcification and roasting of vanadium slag for vanadium extraction, tailings from shale vanadium extraction, and other vanadium-containing minerals. Vanadium and titanium often coexist in minerals, so various vanadium-containing minerals contain varying degrees of titanium. Titanium itself is an important strategic metal, and extracting titanium from vanadium-containing minerals is of great economic significance. The long-term storage of various tailings can cause environmental pollution, and since they cannot be discharged, this creates significant production difficulties. The utilization of vanadium-containing minerals not only recovers valuable elements and avoids resource waste, but also saves costs and significantly reduces environmental pollution.

[0003] Common methods for extracting titanium can be broadly categorized into pyrometallurgy, hydrometallurgy, and selective precipitation separation techniques. Hydrometallurgy primarily uses sulfuric acid, hydrochloric acid, or mixed acids to acidify and decompose slag, increasing the titanium enrichment in the filtrate. The resulting residue can be used for comprehensive cement production. However, its main drawbacks are the large amount of acid used, which can severely corrode equipment. The waste acid produced can easily cause secondary pollution to the surrounding environment, and the waste liquid is extremely difficult to dispose of after use. Pyrometallurgy, on the other hand, utilizes the principle of thermal reduction, carrying out a limited degree of reduction reaction at high temperatures. This is simple to operate, and the final product can be used in cement materials. However, this process compromises titanium enrichment, and subsequent impurity separation is complex and costly, making it difficult to commercialize. Selective precipitation separation technology primarily focuses on titanium enrichment. The key is selecting an optimized titanium-rich phase, requiring the addition of appropriate additives to modify the composition of the titanium dioxide-containing slag. This process offers the advantages of a short and simple process, minimal environmental impact, and the resulting tailings can be used as building materials, among other applications. However, this process suffers from low recovery rates, difficulty growing the enriched phase grains, and high energy consumption.

[0004] Currently, the main methods for recovering titanium and iron from vanadium-containing minerals are the blast furnace method or the pre-reduction-melting method, which involves pelletizing the vanadium slag and pre-reducing it before separating the titanium and iron through electric furnace smelting. Because the 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. Furthermore, the titanium in the titanium-containing slag after smelting mostly exists in the form of pyroxene phases, perovskite, etc., making it difficult to recycle economically. The oxidized pellets of vanadium slag undergo severe reduction expansion and pulverization, making them unsuitable for blast furnace ironmaking. This results in a titanium resource recovery rate of less than 60% in domestic vanadium slag. Vanadium slag abroad, on the other hand, is mainly dumped and discarded, resulting in a serious waste of resources and secondary pollution to the environment. Under the background of "dual carbon" in my country, both the blast furnace method and the pre-reduction-smelting method 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] Patent CN113234935A discloses a method for co-extracting vanadium, titanium, and chromium from vanadium slag. This method selectively reduces pyroxene and fayalite encased in spinel through low-temperature hydrogen reduction, iron removal with ferric chloride, and low-temperature oxalic acid leaching of the vanadium slag, disrupting its structure and dissociating the spinel and silicate phases, fully exposing the spinel phase. Utilizing the acidity and strong complexing properties of oxalic acid, the vanadium slag is directly leached at low temperatures, destroying the spinel structure and allowing the vanadium, titanium, and chromium to complex with oxalate into solution, achieving co-extraction of the three elements. The present invention extracts vanadium, titanium, and chromium from the vanadium slag, achieving leaching rates exceeding 99%. However, this method increases energy consumption, generates waste acid, and takes a long process time.

[0006] Patent CN117737330A discloses a method for recovering iron and titanium from vanadium-extracting slag through hydrogen-based reduction and magnetic separation. The method comprises: preparing raw pellets from the sodium-extracting vanadium-extracting slag through fine grinding, acid leaching, concentration, filtration, and high-pressure roller grinding; directly reducing the raw pellets 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 pellets containing elemental iron and titanium oxide; and crushing, ball milling, fine grinding, and magnetic separation of the reduced pellets 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 hydrothermal organic acid leaching method for vanadium, titanium, and chromium from vanadium, titanium, and chromium raw materials. This method uses high-concentration oxalic acid to directly leach vanadium slag under high temperature and high pressure conditions, achieving the simultaneous extraction of vanadium, titanium, and chromium, thereby addressing the "three wastes" issue. However, this method requires high temperature, high pressure, and high acidity, placing high demands on equipment.

[0008] To effectively recover titanium and iron from vanadium-extraction slag, there is an urgent need to develop an economical, low-energy, and environmentally friendly method for separating titanium from iron. Flotation, as a conventional mineral processing method with high throughput and a short process flow, is becoming increasingly important in mineral separation. Existing research has primarily focused on the flotation of high-grade titanium-containing ores or titanium slag, but limited research has focused on the flotation separation of titanium from vanadium-containing ores. 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 crushes and grades vanadium-containing minerals to obtain mineral powder;

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

[0015] S3 adds an inhibitor and a capture agent to the ore powder for rough separation to obtain a titanium-rich phase 1 and a 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, 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 obtain a particle size ranging from 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 roughing and concentrating flotation time is 5-60 min; and the vanadium mineral content of the roughing and concentrating flotation pulp is 10-50 wt%.

[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 comprises carboxymethyl cellulose and cytidine, 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 ratio of the agents 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 pre-treated by activation, which can improve the adhesion effect of the collector on the surface of the titanium-containing phase. The inhibitors carboxymethyl cellulose and cytidine and the collectors 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. -NH3 +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 between the mineral and the collector molecule, and is less affected by temperature during use. Third, the adsorption of carboxymethyl cellulose on the silicate surface is achieved through the combined action of hydrogen bonding and chemical adsorption. The former is the result of the interaction between the hydroxyl groups in the carboxymethyl cellulose structure and the hydroxyl groups in the silicate structure, while the latter is caused by the interaction between the carboxyl groups of carboxymethyl cellulose and the metal ions on the silicate surface. The amino group and the five-membered ring in cytosine nucleoside can undergo electrostatic adsorption and chemical adsorption with the 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 the collector on its 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 above, so that 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] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are 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 uses a ball mill to mill the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 30 microns as raw material.

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

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

[0039] S4: Add 1000g of 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 pulp for 3 minutes.

[0040] S5: Add 2000g of collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine in a mass ratio of 1:1 into the flotation cell, stir for 1 minute, and adjust the slurry pH to 5; and allow it to react with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape for 10 minutes for a roughing process to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0041] In step S6, the titanium-rich phase 1# prepared in step S5 is used as a raw material, the pH value of the ore pulp is maintained at 5, and the amount of reagent used is 80% of the amount of reagent used in the roughing step, and the titanium-rich phase 1# is fined 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 uses a ball mill to mill the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 60 microns as raw material.

[0047] S2: The powder obtained in step S1 is added to a 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 % in the slurry.

[0049] S4: Add 1000g of 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 1000 g of collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine in a mass ratio of 1:2 into the flotation cell, stir for 1 minute, adjust the slurry pH to 5, and allow it to react with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape for 10 minutes for a roughing process to obtain a titanium-rich phase 1# and a titanium-poor phase 1&.

[0051] In step S6, the titanium-rich phase 1# prepared in step S5 is used as a raw material, the pH value of the ore pulp is maintained at 5, and the amount of reagent used is 80% of the amount of reagent used in the roughing step, and the titanium-rich phase 1# is fined to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

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

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

[0054] Example 3

[0055] The ore sample is vanadium slag from vanadium-titanium magnetite blast furnace smelting, 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 uses a ball mill to mill the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 20 microns as raw material.

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

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

[0060] S4: Add 1000g of 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 1000 g of collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine in a mass ratio of 1:4 into the flotation cell, stir for 1 minute, adjust the slurry pH to 2, and allow it to react with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape for 30 minutes for a roughing process to obtain a titanium-rich phase 1# and a titanium-poor phase 1&.

[0062] In step S6, the titanium-rich phase 1# prepared in step S3 is used as a raw material, the pH value of the ore pulp is maintained at 2, and the amount of reagent used is 80% of the amount of reagent used in the roughing step, and the titanium-rich phase 1# is refined to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

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

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

[0065] Example 4

[0066] The ore sample is vanadium slag from vanadium-titanium magnetite blast furnace smelting, 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 uses a ball mill to mill the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 15 microns as raw material.

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

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

[0071] S4: Add 1500g of 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.

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

[0073] In step S6, the titanium-rich phase 1# prepared in step S3 is used as a raw material, the pH value of the ore pulp is maintained at 1, and the amount of reagents used is 80% of the amount of reagents used in the roughing step, and the titanium-rich phase 1# is fined to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

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

[0075] The purity of the titanium-rich phase 2#TiO2 obtained in this embodiment 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 mill 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 to a mixed solution of 1.5 mol / L sodium sulfite and barium nitrate (mass ratio is 1:2), with a solid-liquid ratio of 1:11, a heating temperature of 65°C, and an activation time of 1.5 h.

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

[0082] S4: Add 800g of 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 react with the flotation pulp for 5 minutes.

[0083] S5: Add 1400 g of collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine in a mass ratio of 1:1 into the flotation cell, stir for 1 minute, adjust the slurry pH to 4, and allow them to react with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape for 50 minutes for a roughing process to obtain a titanium-rich phase 1# and a titanium-poor phase 1&.

[0084] In step S6, the titanium-rich phase 1# prepared in step S3 is used as a raw material, the pH value of the ore pulp is maintained at 4, and the amount of reagents used is 80% of the amount of reagents used in the roughing step, and the titanium-rich phase 1# is finely selected to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0085] S7 repeats the same beneficiation process twice for the titanium-rich phase 2# after the first beneficiation 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 the 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 uses a ball mill to mill the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 15 microns as raw material.

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

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

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

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

[0095] In step S6, the titanium-rich phase 1# prepared in step S3 is used as a raw material, the pH value of the ore pulp is maintained at 3, and the amount of reagents used is 80% of the amount of reagents used in the roughing step, and the titanium-rich phase 1# is refined to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

[0096] S7 repeats the same beneficiation process twice for the titanium-rich phase 2# after the first beneficiation 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 vanadium-titanium magnetite blast furnace smelting, 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 uses a ball mill to mill the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 20 microns as raw material.

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

[0104] S3: Add 1000g of 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.

[0105] S4: Add 1000 g of collector per ton of flotation raw material. Add collectors diethyl phenylphosphonate and 3-chloro-o-anisidine in a mass ratio of 1:4 into the flotation cell, stir for 1 minute, and adjust the slurry pH to 2. Allow the collectors to react with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape for 30 minutes for a roughing process to obtain a titanium-rich phase 1# and a titanium-poor phase 1&.

[0106] In step S5, the titanium-rich phase 1# prepared in step S3 is used as a raw material, the pH value of the ore pulp is maintained at 2, and the amount of reagents used is 80% of the amount of reagents used in the roughing step, and the titanium-rich phase 1# is fined to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

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

[0108] The purity of the titanium-rich phase 2#TiO2 obtained in this comparative example reached 25.32%, and the recovery rate was 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 mill 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 to a mixed solution of 1.5 mol / L sodium sulfite and barium nitrate (mass ratio is 1:2), with a solid-liquid ratio of 1:11, a heating temperature of 65°C, and an activation time of 1.5 h.

[0115] S3: adding water to the activated sample of step S2 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 1400 g of collector per ton of flotation raw material. Add diethyl phenylphosphonate as collector to the flotation cell and stir for 1 minute. Adjust the slurry pH to 4. Allow it to react with the flotation slurry for 3 minutes to effectively capture the titanium-containing phase. Then, aerate for 1 minute and scrape for 50 minutes for a roughing process to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0118] In step S6, the titanium-rich phase 1# prepared in step S3 is used as a raw material, the pH value of the ore pulp is maintained at 4, and the amount of reagents used is 80% of the amount of reagents used in the roughing step, and the titanium-rich phase 1# is finely selected to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

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

[0120] The purity of the titanium-rich phase 2#TiO2 obtained in this comparative example reached 22.27%, and the recovery rate was 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 the 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 uses a ball mill to mill the tailings after calcification roasting and vanadium extraction, and selects powder with a particle size of less than 15 microns as raw material.

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

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

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

[0129] S5: Add 1500g of collector per ton of flotation raw material. Add the collector 3-chloro-o-anisidine to the flotation cell, stir for 1 minute, adjust the pulp pH to 3, and 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 for 40 minutes to perform a roughing operation to obtain titanium-rich phase 1# and titanium-poor phase 1&.

[0130] In step S6, the titanium-rich phase 1# prepared in step S3 is used as a raw material, the pH value of the ore pulp is maintained at 3, and the amount of reagents used is 80% of the amount of reagents used in the roughing step, and the titanium-rich phase 1# is refined to obtain a titanium-rich phase 2# and a titanium-poor phase 2&.

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

[0132] The purity of the titanium-rich phase 2#TiO2 obtained in this comparative example reached 26.32%, and the recovery rate was 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 powder; The S2 mineral powder is activated to obtain mineral powder; the activating agent in the activation treatment 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; S3: Mineral powder is added with water to form a slurry, and an inhibitor and a collector are added to the slurry for rough separation to obtain titanium-rich phase 1 and titanium-poor phase 1; S4 takes the titanium-rich phase 1 as raw material, adds an inhibitor and a collector, and then selects it to obtain the titanium-rich phase 2 and the titanium-poor phase 2; The inhibitors include carboxymethyl cellulose and cytosine nucleoside, and the ratio of the agents is 1:2 to 1:4; the collectors include diethyl phenylphosphonate and 3-chloro-o-anisidine, and the ratio of the agents is 1:1 to 1:

3.

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 mining, smelting and separation process 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, vanadium-containing minerals were crushed and classified, with particle sizes ranging 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 concentration of the activator is 0.5~1.5mol / L.

5. 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 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 1~3 h, the temperature is 40~80 °C, and the solid-liquid ratio is 1:8~1:

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 cleaning pulp is 1-6; the flotation time of the roughing and cleaning is 5-60 min.

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 inhibitor to collector is 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: In S3 and S4, 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: In S3 and S4, the amount of collector added was 1000~2000 g / t.

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