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

Abstract

The invention relates to the technical field of extraction of titanium from vanadium-containing minerals, in particular to a method for separating and extracting valuable metal titanium from vanadium-containing minerals. A method for separating and extracting valuable metal titanium from vanadium-containing minerals comprises the following steps that the vanadium-containing minerals are crushed to obtain first mineral powder, then the first mineral powder is activated, the activated first mineral powder is filtered and dried, and second mineral powder is obtained; and sequentially adding water and a flotation agent into the mineral powder II, and carrying out rough flotation to obtain titanium-rich phase mineral powder I and titanium-poor phase mineral powder I. And sequentially adding water and a flotation agent into the titanium-rich phase mineral powder I, and carrying out fine flotation to obtain titanium-rich phase mineral powder II and titanium-poor phase mineral powder II, and so on. According to the method, through the mineral activation-flotation process, the recovery rate of titanium dioxide in the obtained final titanium-rich phase mineral powder is 64.93%, the grade of titanium dioxide in the recovered titanium-rich phase mineral powder is 48.15%, and the titanium resource in the vanadium-containing mineral can be effectively separated and recovered in a green and efficient mode.

Description

Technical Field

[0001] The invention relates to the technical field of extracting titanium from vanadium-containing minerals, and 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, which may include the following sources: 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. These tailings cannot be discharged directly, but long-term stacking will cause both resource waste and environmental pollution. In vanadium-containing minerals, vanadium and titanium often coexist, so titanium is contained in various vanadium-containing minerals to varying degrees. Titanium itself is also an important strategic metal element, so extracting titanium from vanadium-containing minerals has important economic significance.

[0003] Common methods for extracting titanium include pyrometallurgy, hydrometallurgy, selective precipitation separation technology, etc. Among them, hydrometallurgy mainly uses sulfuric acid, hydrochloric acid, mixed acid, etc. to acid-leach and decompose the slag to increase the titanium content in the filtrate, and the residue obtained can be used for the comprehensive utilization of cement. However, this method of extracting titanium requires a large amount of acid, which will cause serious corrosion to the equipment, and the waste acid produced is easy to cause secondary pollution to the surrounding environment, and the waste liquid after hydrometallurgy is extremely difficult to handle. For pyrometallurgy, it uses the principle of thermal reduction to carry out a certain degree of reduction reaction at high temperature, and the final residue can be used for cement materials. However, for the method of extracting titanium by pyrometallurgy, it will destroy the enrichment of titanium during the extraction process, and the subsequent impurity separation operation is complicated and costly, making this method difficult to use in production. As for the selective precipitation separation technology, it is mainly reflected in the enrichment of titanium, and the key is to select and optimize the titanium-enriched phase, so in this method, it is necessary to add appropriate additives to change the composition of the slag containing titanium dioxide. This process has the advantages of short process, simplicity and low environmental pollution, but the energy consumption of this process is high, the recovery rate of titanium is low, and the collected titanium-enriched phase grains are difficult to grow. In addition, the current recovery methods for extracting titanium and iron from vanadium-containing minerals are mainly blast furnace methods or pre-reduction-melting methods. 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 differentiated during the pre-reduction process, which seriously deteriorates the permeability of the material during subsequent smelting, thereby increasing the energy consumption of smelting. 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. Moreover, the reduction expansion and reduction pulverization of the vanadium slag oxidation pellets are serious, making it also unusable for blast furnace ironmaking. Moreover, the smelting temperature of domestic electric furnace ironmaking is generally about 1500℃~1800℃, the energy consumption of blast furnace process is about 300kgce / t~500kgce / t, and the power consumption of electric furnace smelting process is about 300kWh / t~350kWh / t.

[0004] By searching the existing patents, it is found that the existing patents such as CN 113234935 A disclose a method for co-extracting vanadium, titanium and chromium from vanadium slag. The method selectively reduces the pyroxene and iron olivine wrapped outside the spinel, destroys its structure, realizes the dissociation of the spinel phase and the silicate phase, and fully exposes the spinel phase. Utilizing the acidity and strong complexing property of oxalic acid, the vanadium slag is directly leached at low temperature to destroy the spinel structure, so that the vanadium, titanium and chromium are complexed with oxalate and enter the solution to realize the co-extraction of vanadium, titanium and chromium. However, this method not only increases energy consumption, produces waste acid, but also has a long process time. For example, CN 117737330 A discloses a method for recovering iron and titanium from vanadium slag by hydrogen-based reduction-magnetic separation, comprising: preparing raw balls after fine grinding, acid leaching, concentration, filtration and high-pressure roller grinding of the sodium vanadium slag. The raw balls are directly reduced by oxidation 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. The reduced pellets are crushed, ball milled, finely ground, and magnetically separated to obtain reduced iron powder and high-titanium slag. This method uses a high-temperature process and has high energy consumption costs. For example, CN 111041200A discloses a method for leaching vanadium, titanium, and chromium from vanadium, titanium, and chromium raw materials using a hydrothermal organic acid. This method is to directly leach vanadium slag with high-concentration oxalic acid under high temperature and high pressure conditions to achieve the joint extraction of vanadium, titanium, and chromium, and solve the "three wastes" problem. However, this method needs to be carried out under high temperature, high pressure, and high acidity conditions, and has high requirements for equipment.

[0005] It can be seen from this that the existing method of extracting titanium from vanadium slag has harsh extraction conditions, high energy consumption during the extraction process, and the waste liquid after extraction is prone to cause secondary pollution to the surrounding environment. Summary of the invention

[0006] In order to solve the technical problems in the prior art of extracting titanium from vanadium slag and low-grade vanadium-containing minerals, such as harsh extraction conditions, high energy consumption and the generated waste liquid easily causing secondary pollution to the surrounding environment, the present invention provides a method for separating and extracting valuable metal titanium from vanadium-containing minerals.

[0007] The present invention is implemented by the following technical scheme: a method for separating and extracting valuable metal titanium from vanadium-containing minerals, which comprises the following steps: S1: crushing the vanadium-containing mineral to obtain mineral powder one, and activating the mineral powder one by an activator.

[0008] S2: Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Then add water to the mineral powder 2 to form slurry 1, add a flotation agent to the slurry 1, adjust the pH and stir thoroughly, and perform rough flotation on the slurry mixture 1 while stirring, and obtain titanium-rich phase ore powder 1 and titanium-poor phase ore powder 1 after rough flotation.

[0009] S3: adding water to the titanium-rich phase ore powder 1 to form ore slurry 2, then adding a flotation agent to the ore slurry 2, adjusting the pH and stirring sufficiently, and performing fine flotation on the ore slurry mixture 2 while stirring, to obtain titanium-rich phase ore powder 2 and titanium-poor phase ore powder 2 after fine flotation.

[0010] S4: Repeat step S3 for multiple times, and finally obtain titanium-rich phase ore powder with a titanium dioxide grade higher than 45%.

[0011] The flotation agent includes an inhibitor and a collector. The inhibitor includes carboxymethyl cellulose and cytosine nucleoside. The collector includes diethyl phenylphosphonate and 3-chloro-o-anisidine. The amount of the flotation agent added in step S3 is 80% of the amount of the flotation agent added in step S2.

[0012] As a further improvement of the present invention, the mass ratio of the inhibitor to the collector is 1:1 to 1:4;

[0013] As a further improvement of the present invention, the mass ratio of carboxymethyl cellulose to cytosine nucleoside is 1:2 to 1:4.

[0014] As a further improvement of the present invention, the mass ratio of diethyl phenylphosphonate to 3-chloro-o-anisidine is 1:1 to 1:3.

[0015] As a further improvement of the present invention, the particle size range of the mineral powder obtained by the crushing process is 1 μm to 74 μm.

[0016] As a further improvement of the present invention, the concentration of the activator is 0.5 mol / L-1.5 mol / L, the activation time is 1 h to 3 h, and the activation temperature is 40° C. to 80° C.

[0017] As a further improvement of the present invention, the activator includes any one of sulfuric acid, sulfurous acid, sodium sulfate, copper sulfate, oxalic acid, lime, sulfur dioxide, lead nitrate, sodium carbonate, sodium hydroxide, lead salts, and barium salts, or a mixture of any two or more thereof.

[0018] As a further improvement of the present invention, the solid-liquid ratio of the activator to the mineral powder is 1:8 to 1:15.

[0019] As a further improvement of the present invention, the pH range after adjustment in step S2 and step S3 is both 1 to 6; and the stirring time is both 3 min to 5 min.

[0020] As a further improvement of the present invention, the mass percentage of the mineral powder 2 in the ore slurry 1 is 10% to 50%. The mass percentage of the titanium-rich phase mineral powder 1 in the ore slurry 2 is 10% to 50%.

[0021] As a further improvement of the present invention, the flotation time of rough flotation and fine flotation is 5 minutes to 60 minutes.

[0022] As a further improvement of the present invention, in step S2, the amount of inhibitor added is 500g to 2000g per ton of mineral powder II; the amount of collector added is 1000g to 2000g per ton of mineral powder II.

[0023] As a further improvement of the present invention, in step S3, the amount of inhibitor added is 500g to 2000g per ton of titanium-rich phase ore powder; the amount of collector added is 1000g to 2000g per ton of titanium-rich phase ore powder.

[0024] As a further improvement of the present invention, in step S3, the amount of inhibitor added is 500g to 2000g per ton of titanium-rich phase ore powder; the amount of collector added is 1000g to 2000g per ton of titanium-rich phase ore powder.

[0025] As a further improvement of the present invention, the vanadium-containing minerals include any one or a mixture of any two or more of the intermediates or tailings produced in the mining, smelting and sorting process of vanadium-titanium magnetite, the tailings produced by calcification roasting and vanadium extraction of vanadium slag, and the tailings produced in the process of shale vanadium extraction.

[0026] The technical solution provided by the present invention has the following beneficial effects:

[0027] (1) The method for separating and extracting valuable metal titanium from vanadium-containing minerals provided by the present invention uses a mineral activation-flotation process to achieve a recovery rate of titanium dioxide in the recovered titanium-rich phase ore powder of 64.93% and a grade of titanium dioxide in the recovered titanium-rich phase ore powder of 48.15%, thereby being able to achieve green and efficient separation and recovery of titanium resources in vanadium-containing minerals.

[0028] (2) The method for separating and extracting valuable metal titanium from vanadium-containing minerals provided by the present invention is to first activate the vanadium-containing mineral, then select carboxymethyl cellulose and cytosine nucleoside as inhibitors, and diethyl phenylphosphonate and 3-chloro-o-anisidine as collectors. Through the chemical reaction between the activator and the surface of the vanadium-containing mineral, the collector added later can be more easily adsorbed on the surface of the titanium-containing ore phase mineral, and the activator can also react with the non-titanium-containing phase, and then the non-titanium-containing phase mineral is contacted with the surface of the inhibitor to inhibit the floating of the non-titanium-containing phase mineral. Through the synergistic effect of the activator, the inhibitor and the collector, the separation effect of the titanium-containing phase mineral and the non-titanium-containing phase mineral in the flotation process can be further improved. In addition, the inhibitor and the collector in this embodiment can effectively expand the difference in floatability between the titanium-containing phase mineral and the non-titanium-containing phase mineral in the vanadium-containing mineral, thereby improving the extraction efficiency of the titanium element in the flotation process. At the same time, the inhibitor and the collector in this embodiment are both environmentally friendly, and will not cause pollution to the environment during the extraction process, which meets the needs of green chemistry.

[0029] (3) The method for separating and extracting valuable metal titanium from vanadium-containing minerals provided by the present invention has the following advantages by selecting an activator to activate the mineral powder one: (a) Through the chemical reaction between the activator and the surface of the mineral powder one, the collector added subsequently is more easily adsorbed on the surface of the titanium-containing ore. (b) The activator can also increase the Zeta potential of the titanium-containing phase by affecting the pH, thereby hindering the production of hydrophilic substances. (c) The activator can remove the hydrophilic hydroxides and complexes adsorbed on the surface of the titanium-containing phase ore in the mineral powder one, exposing the fresh surface of the titanium-containing ore. (d) The activator can react with the insoluble sulfate in the mineral powder one to produce soluble substances, thereby reducing the interference of gangue minerals in the mineral powder one. (e) The activator can adsorb on the surface of the gangue mineral in the mineral powder one, increase new active sites, and expand the floatability difference between the titanium-containing ore and the gangue mineral in the mineral powder one, thereby promoting the separation of the titanium-containing ore and the gangue mineral. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a flow chart of a method for separating and extracting valuable metal titanium from vanadium-containing minerals provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0031] The present invention is further described below in conjunction with specific implementation methods. It should be noted that, under the premise of no conflict, the various embodiments or technical features described below can be arbitrarily combined to form a new embodiment.

[0032] In the description of the present invention, it should be noted that for directional words, such as the terms "center", "lateral", "longitudinal", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise" and the like indicating directions and positional relationships are based on the directions or positional relationships shown in the drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific direction, be constructed and operated in a specific direction, and cannot be understood as limiting the specific protection scope of the present invention. The terms "first", "second", etc. in the specification and claims of the present invention are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. The terms "including" and "having" in the specification and claims of the present invention and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device including a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0033] Example 1

[0034] This embodiment provides a method for separating and extracting valuable metal titanium from vanadium-containing minerals. Figure 1 , which comprises the following steps:

[0035] S1: crushing the vanadium-containing mineral to obtain a mineral powder 1, and activating the mineral powder 1 with an activator.

[0036] In step S1, the vanadium-containing mineral can be crushed and graded by a ball mill to obtain a mineral powder with a certain particle size. The activator can be selected from sulfuric acid, sulfurous acid, sodium sulfide, copper sulfate, oxalic acid, lime, sulfur dioxide, lead nitrate, sodium carbonate, sodium hydroxide, lead salt, barium salt or a mixture of multiple thereof.

[0037] The activator can also be a mixture of one or more of oxalic acid, barium nitrate and barium acetate.

[0038] In this embodiment, the purpose of using an activator to activate the mineral powder is: (1) through the chemical reaction between the activator and the surface of the mineral powder, the collector added later is more easily adsorbed on the surface of the titanium-containing ore. (2) The activator can also increase the Zeta potential of the titanium-containing phase by affecting the pH, thereby hindering the production of hydrophilic substances. (3) The activator can remove the hydrophilic hydroxides and complexes adsorbed on the surface of the titanium-containing phase ore in the mineral powder, exposing the fresh surface of the titanium-containing ore. (4) The activator can react with the insoluble sulfate in the mineral powder to produce soluble substances, thereby reducing the interference of gangue minerals in the mineral powder. (5) The activator can adsorb on the surface of the gangue mineral in the mineral powder, increase new active sites, expand the floatability difference between the titanium-containing ore and the gangue mineral in the mineral powder, and promote the separation of the titanium-containing ore and the gangue mineral.

[0039] For example, sodium carbonate activator can react with insoluble sulfate in mineral powder to generate soluble carbonate, thereby achieving the purpose of removing sulfur and promoting the flotation separation of titanium-containing ore phase.

[0040] In step S1, the concentration of the activator can be 0.5 mol / L-1.5 mol / L, the activation time can be 1 h-3 h, and the activation temperature can be 40° C.-80° C. The solid-liquid ratio of the activator to the mineral powder can be 1:8-1:15.

[0041] In this embodiment, the particle size of the prepared mineral powder 1 may range from 1 μm to 74 μm.

[0042] S2: Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Then pour the mineral powder 2 into the flotation machine, and add water to the flotation machine to form slurry 1. The ratio between the amount of water added and the amount of mineral powder 2 is 1:1 to 9:1, so that the mass percentage of mineral powder 2 in slurry 1 can be between 10% and 50%. The water in the above ratio can save water resources while meeting the requirements for rough flotation of mineral powder 2. Add flotation agent to slurry 1, adjust the pH to 1-6 and stir thoroughly. After adding the flotation agent, two parts of products will be produced in the flotation machine, one part is formed by foam floating, and the other is left in the slurry mixture 1. The whole rough flotation time can be 5min-60min. In this process, the flotation agent can be stirred for 3min to 5min after adding. Then start the scraper of the flotation agent, and then the products that form foam floating can be scraped off and collected uniformly by the scraper on the flotation machine while stirring. The collected products that form foam and float on the surface are filtered and dried in sequence to obtain titanium-rich phase ore powder 1, and the slurry mixture 1 in the flotation machine is filtered and dried in sequence to obtain titanium-poor phase ore powder 1. Through the above operation, titanium-rich phase ore powder 1 and titanium-poor phase ore powder 1 are obtained after rough flotation.

[0043] In this embodiment, the flotation agent includes a suppressor and a collector. The mass ratio of the suppressor to the collector is 1:1 to 1:4. The suppressor includes carboxymethyl cellulose and cytosine nucleoside. The mass ratio of carboxymethyl cellulose to cytosine nucleoside is 1:2 to 1:4. The collector includes diethyl phenylphosphonate and 3-chloro-o-anisidine.

[0044] In this embodiment, when adding a flotation agent, an inhibitor may be first added to the slurry one, and then a collector may be added after sufficient stirring. After adding the collector, the pH is adjusted and the mixture is sufficiently stirred. The purpose of adding the inhibitor is to inhibit the floating of non-titanium-containing phase minerals in the slurry mixture one, thereby enhancing the separation of titanium-containing phase minerals and non-titanium-containing phase minerals during the flotation process. The purpose of adding the collector is that the collector can be adsorbed on the surface of the titanium-containing phase ore in the slurry mixture one, so that the titanium-containing phase ore has hydrophobicity, thereby achieving the separation of the titanium-containing phase ore from other mineral phases. The amount of the inhibitor added is 500g to 2000g per ton of mineral powder two; the amount of the collector added is 1000g to 2000g per ton of mineral powder two.

[0045] Among them, the carboxymethyl cellulose in the inhibitor is used to adsorb on the surface of silicate in non-titanium phase minerals. The adsorption of the inhibitor on the silicate surface is achieved through the combined action of hydrogen bonding and chemical adsorption. Adsorption through hydrogen bonding is the result of the action of hydroxyl groups in the carboxymethyl cellulose structure and hydroxyl groups in the silicate structure, while chemical adsorption is caused by the action of carboxymethyl cellulose and metal ions on the silicate surface. Under the combined action of hydrogen bonding and chemical adsorption, the inhibitor can inhibit the floating of non-titanium phase minerals in the slurry mixture, thereby improving the separation of titanium-containing phase minerals and non-titanium phase minerals. Furthermore, the amino group and the five-membered ring in the cytosine nucleoside in the inhibitor can both electrostatically adsorb and chemically adsorb metal ions in non-titanium phase minerals. Therefore, in this embodiment, by selecting carboxymethyl cellulose and cytosine nucleoside as inhibitors, the two can further inhibit the floating of non-titanium phase minerals through synergistic action, and improve the separation effect of non-titanium phase minerals and titanium-containing phase minerals in the slurry mixture.

[0046] As for the collector, the oxygen atom in the phosphonic acid group of diethyl phenylphosphonate in the collector can form a four-membered chelate ring or an insoluble compound with the unsaturated lattice cations on the surface of the titanium-containing phase mineral in the slurry mixture. And diethyl phenylphosphonate can chemically interact with the titanium site in the titanium-containing phase mineral to form a hydrophobic organic phosphonate at the solid-liquid interface. As a result, the collector can capture the titanium-containing mineral in the slurry mixture and float it up by flotation to achieve separation from the non-titanium phase minerals in the slurry mixture. At the same time, the amine group in the amine in 3-chloro-o-anisidine is hydrolyzed in water to form -NH 3+ This positively charged group adsorbs on the surface of the titanium-containing mineral in the slurry mixture, and the hydroxyl group in 3-chloro-o-anisidine has strong hydrophobicity, making the surface of the titanium-containing mineral hydrophobic, while -NH 3+ The group can effectively capture titanium-containing phase minerals. Through the combined action of the amine group and the hydroxyl group, 3-chloro-o-anisidine can have strong semi-micelle adsorption on the surface of the titanium-containing phase mineral, further forming an adsorption group between 3-chloro-o-anisidine and the titanium-containing mineral, thereby improving the capture effect of the collector on the titanium-containing phase. In addition, 3-chloro-o-anisidine is less affected by temperature during use and has high stability.

[0047] S3: Add water to the titanium-rich phase ore powder 1 obtained in step S2 to form ore pulp 2. The ratio between the amount of water added and the amount of titanium-rich phase ore powder 1 is 1:1 to 1:9. Then add a flotation agent to the ore pulp 2, adjust the pH to 1-6 and stir thoroughly. After adding the flotation agent, two parts of products will be produced in the flotation machine, one part is formed by foam floating, and the other is left in the ore pulp mixture 2. The time of the entire rough flotation can be 5min-60min. In this process, the flotation agent can be added and stirred for 3min to 5min. Then start the scraper of the flotation machine, and then the scraper on the flotation machine can be used to scrape off the products that form foam floating while stirring and collect them uniformly. The collected products that form foam floating are filtered and dried in turn to obtain titanium-rich phase ore powder 2, and the ore pulp mixture 2 in the flotation machine is filtered and dried in turn to obtain titanium-poor phase ore powder 2. Through the above operation, titanium-rich phase ore powder 2 and titanium-poor phase ore powder 2 are obtained after fine flotation.

[0048] In this embodiment, the amount of flotation agent added in step S3 can be 80% of the amount of flotation agent added in step S2. The time of fine flotation can also be between 5min and 60min. In this step, the amount of inhibitor added is 500g to 2000g per ton of titanium-rich phase ore powder 1; the amount of collector added is 1000g to 2000g per ton of titanium-rich phase ore powder 1.

[0049] S4: Repeat step S3 for many times, and finally obtain titanium-rich phase ore powder with a titanium dioxide grade of not less than 45%, which meets the industry standard. The industry standard may be the ferrous metallurgy industry standard of the People's Republic of China YB / T 4031-2015.

[0050] Among them, in this embodiment, the vanadium-containing mineral can be any one of the intermediates or tailings produced in the mining, smelting and sorting process of vanadium-titanium magnetite, the intermediates or tailings produced in the mining, smelting and sorting process of vanadium-titanium magnetite, the tailings produced by calcification roasting of vanadium slag to extract vanadium, and the tailings produced in the process of shale vanadium extraction, or a mixture of any two or more thereof.

[0051] In this embodiment, through the mineral activation-flotation process, the recovery rate of titanium dioxide in the recovered titanium-rich phase ore powder is 60.58% and the grade of titanium dioxide in the recovered titanium-rich phase ore powder is 46.75%, which can achieve green and efficient separation and recovery of titanium resources in vanadium-containing minerals.

[0052] In the present embodiment, by first activating the vanadium-containing mineral, then by selecting carboxymethyl cellulose and cytosine nucleoside as inhibitors, diethyl phenylphosphonate and 3-chloro-o-anisidine as collectors. Through the chemical action of the activator and the surface of the vanadium-containing mineral, the collector added later can be more easily adsorbed on the surface of the titanium-containing ore phase mineral, and the activator can also react with the non-titanium-containing phase, and then the surface contact of the inhibitor with the non-titanium-containing phase mineral suppresses the floating of the non-titanium-containing phase mineral. Under the synergistic effect of the activator, the inhibitor and the collector, the separation effect of the titanium-containing phase mineral and the non-titanium-containing phase mineral in the flotation process can be further improved. In addition, the inhibitor and the collector in the present embodiment can effectively expand the difference in floatability between the titanium-containing phase mineral and the non-titanium-containing phase mineral in the vanadium-containing mineral, thereby improving the extraction efficiency of the titanium element in the flotation process, and the inhibitor and the collector in the present embodiment are both selected to be environmentally friendly, and will not cause pollution to the environment during the extraction process, which meets the needs of green chemistry.

[0053] In this embodiment, the recovery rate Y of titanium dioxide in the titanium-rich phase ore powder 2 is calculated as follows: Where a is the amount of titanium dioxide in the vanadium-containing mineral to be extracted, and b is the amount of titanium dioxide in the titanium-rich phase II ore powder. The grade of titanium dioxide in the titanium-rich phase II ore powder is W TiO2 It can be measured by chemical titration.

[0054] Next, the applicant selected different types of vanadium-containing minerals to extract titanium using the above method. The specific extraction process can be referred to the following Examples 2 to 7.

[0055] Example 2

[0056] In this embodiment, the ore sample is the tailings after vanadium slag is subjected to calcination roasting and sulfuric acid acid leaching to extract vanadium. The grade of titanium dioxide in the tailings is W TiO2 =8.67%.

[0057] The above tailings are extracted with titanium by the following extraction method, and the specific extraction operation is as follows:

[0058] (1) The tailings after calcination roasting and sulfuric acid leaching for vanadium extraction are ball milled in a ball mill, and the powder with a particle size of less than 30 μm is selected as the first mineral powder.

[0059] (2) Adding the mineral powder 1 into a 1 mol / L barium nitrate solution for activation, the solid-liquid ratio of the mineral powder 1 to the barium nitrate solution is 1:10, the activation temperature is 70° C., and the activation time is 2 h.

[0060] (3) Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Put the mineral powder 2 into a flotation tank in a flotation machine, and then add water to the mineral powder 2 to obtain slurry 1. The amount of water added is such that the mass proportion of the mineral powder 2 in the slurry 1 is 10%.

[0061] (4) Carboxymethyl cellulose and cytosine nucleoside, which are inhibitors, are added to the flotation tank at a rate of 1000 g per ton of mineral powder No. 2. The mass ratio of carboxymethyl cellulose to cytosine nucleoside is 1:2. After adding the inhibitor, the inhibitor is allowed to react with the ore pulp No. 1 for 3 minutes. Then, diethyl phenylphosphonate and 3-chloro-o-anisidine are added to the flotation tank at a rate of 2000 g per ton of mineral powder No. 2. The mass ratio of diethyl phenylphosphonate to 3-chloro-o-anisidine is 1:1. After stirring for 1 minute, the pH is adjusted to 5; and the added collector is allowed to react with the ore pulp No. 1 for 3 minutes, and then the flotation tank is aerated for 1 minute and then scraped. After scraping for 10 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder No. 1, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder No. 1.

[0062] (5) The titanium-rich phase ore powder 1 obtained in step (4) is placed in a flotation tank as a raw material, and then water is added to the titanium-rich phase ore powder 1 to obtain slurry 2, wherein the amount of water added is such that the mass proportion of the titanium-rich phase ore powder 1 in the slurry 2 is 10%.

[0063] (6) 800 g of inhibitor was added to each ton of titanium-rich phase ore powder 1, and then inhibitors carboxymethyl cellulose and cytosine nucleoside were added to the flotation tank. The mass ratio of carboxymethyl cellulose to cytosine nucleoside was 1:2. After adding the inhibitor, it was allowed to react with the ore pulp 1 for 3 minutes. Then 1600 g of collector was added to each ton of titanium-rich phase ore powder 1, and diethyl phenylphosphonate and 3-chloro-o-anisidine were added to the flotation tank. The mass ratio of diethyl phenylphosphonate to 3-chloro-o-anisidine was 1:1. After stirring for 1 minute, the pH was adjusted to 5; and the added collector was allowed to react with the ore pulp 1 for 3 minutes, and then the flotation tank was aerated for 1 minute and then scraped. After scraping for 10 minutes, the foamed product was filtered and dried in turn to obtain titanium-rich phase ore powder 2, and the ore pulp mixture remaining in the flotation tank was filtered and dried in turn to obtain titanium-poor phase ore powder 2.

[0064] (7) Repeating the operations of step (5) and step (6) four times on the titanium-rich phase ore powder 2 after being selected and dried in step (6) to obtain titanium-rich phase ore powder 6 and titanium-poor phase ore powder 6. The recovery rate of titanium dioxide in the titanium-rich phase ore powder finally obtained is 61.53% and the grade of titanium dioxide is 47.59%.

[0065] Example 3

[0066] In this embodiment, the ore sample is the tailings after vanadium slag is roasted with sodium and leached with sulfuric acid to extract vanadium. The grade of titanium dioxide in the tailings is W TiO2 =9.46%.

[0067] The above tailings are extracted with titanium by the following extraction method, and the specific extraction operation is as follows:

[0068] (1) The tailings after sodium roasting and sulfuric acid leaching for vanadium extraction are ball milled in a ball mill, and the powder with a particle size of less than 60 μm is selected as the first mineral powder.

[0069] (2) Add 1 mol / L lead acetate solution to activate the mineral powder 1, the solid-liquid ratio of the mineral powder 1 to the barium nitrate solution is 1:8, the activation temperature is 65°C, and the activation time is 3 h.

[0070] (3) Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Put the mineral powder 2 into a flotation cell in a flotation machine, and then add water to the mineral powder 2 to obtain slurry 1. The amount of water added is such that the mass proportion of the mineral powder 2 in the slurry 1 is 20%.

[0071] (4) 1000g of inhibitor is added to each ton of mineral powder 2, and then inhibitors carboxymethyl cellulose and cytosine nucleoside are added to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:3. After adding the inhibitor, it is allowed to react with the ore pulp 1 for 5 minutes. Then, 1000g of collector is added to each ton of mineral powder 2, and diethyl phenylphosphonate and 3-chloro-o-anisidine are added to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:2. After stirring for 1 minute, the pH is adjusted to 5; and the added collector is allowed to react with the ore pulp 1 for 3 minutes, and then the flotation tank is aerated for 1 minute and then scraped. After scraping for 10 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder 1, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder 1.

[0072] (5) The titanium-rich phase ore powder 1 obtained in step (4) is placed in a flotation tank as a raw material, and then water is added to the titanium-rich phase ore powder 1 to obtain slurry 2, wherein the amount of water added is such that the mass proportion of the titanium-rich phase ore powder 1 in the slurry 2 is 20%.

[0073] (6) Add 800g of inhibitor to each ton of titanium-rich phase ore powder one, and add inhibitors carboxymethyl cellulose and cytosine nucleoside to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:3. After adding the inhibitor, let it react with the ore pulp one for 3 minutes. Then add 800g of collector to each ton of titanium-rich phase ore powder one, and add diethyl phenylphosphonate and 3-chloro-o-anisidine to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:2. After stirring for 1 minute, adjust the pH to 5; and let the added collector react with the ore pulp one for 3 minutes, then aerate the flotation tank for 1 minute and scrape the foam. After scraping the foam for 10 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder two, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder two.

[0074] (7) Repeating the operations of step (5) and step (6) four times on the titanium-rich phase ore powder 2 after being selected and dried in step (6) to obtain titanium-rich phase ore powder 6 and titanium-poor phase ore powder 6. The recovery rate of titanium dioxide in the titanium-rich phase ore powder finally obtained is 62.41% and the grade of titanium dioxide is 46.20%.

[0075] Example 4

[0076] In this embodiment, the ore sample comes from the vanadium slag after smelting vanadium-titanium magnetite blast furnace, and the grade of titanium dioxide in the tailings is W TiO2 =5.75%.

[0077] The above tailings are extracted with titanium by the following extraction method, and the specific extraction operation is as follows:

[0078] (1) The vanadium slag after smelting vanadium-titanium magnetite blast furnace is ball milled with a ball mill, and powder with a particle size less than 20 μm is selected as mineral powder 1.

[0079] (2) Adding the mineral powder 1 into a mixed solution of 0.5 mol / L sodium sulfite and sodium carbonate for activation, the solid-liquid ratio of the mineral powder 1 to the barium nitrate solution is 1:12, the activation temperature is 55° C., and the activation time is 3 h.

[0080] (3) Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Put the mineral powder 2 into a flotation tank in a flotation machine, and then add water to the mineral powder 2 to obtain slurry 1. The amount of water added is such that the mass proportion of the mineral powder 2 in the slurry 1 is 25%.

[0081] (4) 1000g of inhibitor is added to each ton of mineral powder 2, and then inhibitors carboxymethyl cellulose and cytosine nucleoside are added to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:3. After adding the inhibitor, it is allowed to react with the ore pulp 1 for 5 minutes. Then, 1000g of collector is added to each ton of mineral powder 2, and diethyl phenylphosphonate and 3-chloro-o-anisidine are added to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:4. After stirring for 1 minute, the pH is adjusted to 2; and the added collector is allowed to react with the ore pulp 1 for 3 minutes, and then the flotation tank is aerated for 1 minute and then scraped. After scraping for 10 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder 1, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder 1.

[0082] (5) The titanium-rich phase ore powder 1 obtained in step (4) is placed in a flotation tank as a raw material, and then water is added to the titanium-rich phase ore powder 1 to obtain slurry 2, wherein the amount of water added is such that the mass proportion of the titanium-rich phase ore powder 1 in the slurry 2 is 25%.

[0083] (6) Add 800g of inhibitor to each ton of titanium-rich phase ore powder one, and add inhibitors carboxymethyl cellulose and cytosine nucleoside to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:3. After adding the inhibitor, let it react with the ore pulp one for 3 minutes. Then add 800g of collector to each ton of titanium-rich phase ore powder one, and add diethyl phenylphosphonate and 3-chloro-o-anisidine to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:4. After stirring for 1 minute, adjust the pH to 2; and let the added collector react with the ore pulp one for 3 minutes, then aerate the flotation tank for 1 minute and scrape the foam. After scraping the foam for 10 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder two, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder two.

[0084] (7) Repeating the operations of step (5) and step (6) five times on the titanium-rich phase ore powder 2 after being selected and dried in step (6) to obtain titanium-rich phase ore powder 7 and titanium-poor phase ore powder 7. The recovery rate of titanium dioxide in the titanium-rich phase ore powder finally obtained is 60.36% and the grade of titanium dioxide is 47.71%.

[0085] Example 5

[0086] In this embodiment, the ore sample comes from the vanadium slag after smelting vanadium-titanium magnetite blast furnace, and the grade of titanium dioxide in the tailings is W TiO2 =5.75%.

[0087] The above tailings are extracted with titanium by the following extraction method, and the specific extraction operation is as follows:

[0088] (1) The vanadium slag after smelting vanadium-titanium magnetite blast furnace is ball milled with a ball mill, and powder with a particle size less than 15 μm is selected as mineral powder 1.

[0089] (2) Add the mineral powder 1 into a mixed solution of 0.5 mol / L sodium sulfite and lead nitrate for activation, the solid-liquid ratio of the mineral powder 1 to the barium nitrate solution is 1:12, the activation temperature is 45° C., and the activation time is 2 h.

[0090] (3) Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Put the mineral powder 2 into a flotation tank in a flotation machine, and then add water to the mineral powder 2 to obtain slurry 1. The amount of water added is such that the mass proportion of the mineral powder 2 in the slurry 1 is 30%.

[0091] (4) 1500g of inhibitor is added to each ton of mineral powder 2, and then inhibitors carboxymethyl cellulose and cytosine nucleoside are added to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:3. After adding the inhibitor, it is allowed to react with the ore pulp 1 for 5 minutes. Then, 1800g of collector is added to each ton of mineral powder 2, and diethyl phenylphosphonate and 3-chloro-o-anisidine are added to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:4. After stirring for 1 minute, the pH is adjusted to 1; and the added collector is allowed to react with the ore pulp 1 for 3 minutes, and then the flotation tank is aerated for 1 minute and then scraped. After scraping for 30 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder 1, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder 1.

[0092] (5) The titanium-rich phase ore powder 1 obtained in step (4) is placed in a flotation tank as a raw material, and then water is added to the titanium-rich phase ore powder 1 to obtain slurry 2, wherein the amount of water added is such that the mass proportion of the titanium-rich phase ore powder 1 in the slurry 2 is 30%.

[0093] (6) 1200g of inhibitor is added to each ton of titanium-rich phase ore powder one, and then inhibitors carboxymethyl cellulose and cytosine nucleoside are added to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:3. After adding the inhibitor, it is allowed to react with the ore pulp one for 3 minutes. Then, 1440g of collector is added to each ton of titanium-rich phase ore powder one, and diethyl phenylphosphonate and 3-chloro-o-anisidine are added to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:4. After stirring for 1 minute, the pH is adjusted to 1; and the added collector is allowed to react with the ore pulp one for 3 minutes, and then the flotation tank is aerated for 1 minute and then scraped. After scraping for 30 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder two, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder two.

[0094] (7) Repeating the operations of step (5) and step (6) five times on the titanium-rich phase ore powder 2 after being selected and dried in step (6) to obtain titanium-rich phase ore powder 7 and titanium-poor phase ore powder 7. The recovery rate of titanium dioxide in the titanium-rich phase ore powder finally obtained is 64.93% and the grade of titanium dioxide is 48.15%.

[0095] Example 6

[0096] In this embodiment, the ore sample comes from the tailings of stone coal vanadium ore after roasting and acid leaching to extract vanadium. The grade of titanium dioxide in the tailings is W TiO2 =6.28%.

[0097] The above tailings are extracted with titanium by the following extraction method, and the specific extraction operation is as follows:

[0098] (1) The tailings of the stone coal vanadium ore after roasting and acid leaching to extract vanadium are ball milled in a ball mill, and the powder with a particle size less than 35 μm is selected as the first mineral powder.

[0099] (2) Adding the mineral powder 1 into a mixed solution of 1.5 mol / L sodium sulfite and barium nitrate for activation, the solid-liquid ratio of the mineral powder 1 to the barium nitrate solution is 1:11, the activation temperature is 65° C., and the activation time is 1.5 h.

[0100] (3) Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Put the mineral powder 2 into a flotation cell in a flotation machine, and then add water to the mineral powder 2 to obtain slurry 1. The amount of water added is such that the mass proportion of the mineral powder 2 in the slurry 1 is 35%.

[0101] (4) Carboxymethyl cellulose and cytosine nucleoside, which are inhibitors, are added to the flotation tank at a rate of 800 g per ton of mineral powder No. 2. The mass ratio of carboxymethyl cellulose to cytosine nucleoside is 1:4. After adding the inhibitor, the inhibitor is allowed to react with the ore pulp No. 1 for 5 minutes. Then, diethyl phenylphosphonate and 3-chloro-o-anisidine are added to the flotation tank at a rate of 1400 g per ton of mineral powder No. 2. The mass ratio of diethyl phenylphosphonate to 3-chloro-o-anisidine is 1:1. After stirring for 1 minute, the pH is adjusted to 4; the added collector is allowed to react with the ore pulp No. 1 for 3 minutes, and then the flotation tank is aerated for 1 minute and then scraped. After scraping for 50 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder No. 1, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder No. 1.

[0102] (5) The titanium-rich phase ore powder 1 obtained in step (4) is placed in a flotation tank as a raw material, and then water is added to the titanium-rich phase ore powder 1 to obtain slurry 2, wherein the amount of water added is such that the mass proportion of the titanium-rich phase ore powder 1 in the slurry 2 is 35%.

[0103] (6) Add 640g of inhibitor to each ton of titanium-rich phase ore powder one, and then add inhibitors carboxymethyl cellulose and cytosine nucleoside to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:4. After adding the inhibitor, let it react with the ore pulp one for 3 minutes. Then add 1120g of collector to each ton of titanium-rich phase ore powder one, add diethyl phenylphosphonate and 3-chloro-o-anisidine to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:1. After stirring for 1 minute, adjust the pH to 4; and let the added collector react with the ore pulp one for 3 minutes, then aerate the flotation tank for 1 minute and scrape the foam. After scraping the foam for 50 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder two, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder two.

[0104] (7) Repeating the operations of step (5) and step (6) four times on the titanium-rich phase ore powder 2 after being selected and dried in step (6) to obtain titanium-rich phase ore powder 6 and titanium-poor phase ore powder 6. The recovery rate of titanium dioxide in the titanium-rich phase ore powder finally obtained is 64.93% and the grade of titanium dioxide is 48.15%.

[0105] Example 7

[0106] In this embodiment, the ore sample comes from the tailings after direct acid leaching of vanadium from stone coal vanadium ore. The grade of titanium dioxide in the tailings is W TiO2 =7.44%.

[0107] The above tailings are extracted with titanium by the following extraction method, and the specific extraction operation is as follows:

[0108] (1) The tailings after direct acid leaching of vanadium from stone coal vanadium ore are ball milled with a ball mill, and powder with a particle size of less than 15 μm is selected as mineral powder 1.

[0109] (2) Add the mineral powder 1 into a 1 mol / L mixed solution of barium nitrate, sodium carbonate and lead acetate for activation, the solid-liquid ratio of the mineral powder 1 to the barium nitrate solution is 1:12, the activation temperature is 50° C., and the activation time is 1.5 h.

[0110] (3) Filter and dry the activated mineral powder 1 to obtain mineral powder 2. Put the mineral powder 2 into a flotation cell in a flotation machine, and then add water to the mineral powder 2 to obtain slurry 1. The amount of water added is such that the mass proportion of the mineral powder 2 in the slurry 1 is 40%.

[0111] (4) Carboxymethyl cellulose and cytosine nucleoside, which are inhibitors, are added to the flotation tank at a rate of 800 g per ton of mineral powder No. 2. The mass ratio of carboxymethyl cellulose to cytosine nucleoside is 1:3. After adding the inhibitor, it is allowed to react with the ore pulp No. 1 for 4 minutes. Then, 1500 g of collector is added to the flotation tank at a rate of 1500 g per ton of mineral powder No. 2. The mass ratio of diethyl phenylphosphonate to 3-chloro-o-anisidine is 1:4. After stirring for 1 minute, the pH is adjusted to 3; and the added collector is allowed to react with the ore pulp No. 1 for 4 minutes, and then the flotation tank is aerated for 1 minute and then scraped. After scraping for 40 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder No. 1, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder No. 1.

[0112] (5) The titanium-rich phase ore powder 1 obtained in step (4) is placed in a flotation tank as a raw material, and then water is added to the titanium-rich phase ore powder 1 to obtain slurry 2, wherein the amount of water added is such that the mass proportion of the titanium-rich phase ore powder 1 in the slurry 2 is 40%.

[0113] (6) Add 640g of inhibitor to each ton of titanium-rich phase ore powder one, and add inhibitors carboxymethyl cellulose and cytosine nucleoside to the flotation tank. Among them, the mass ratio of carboxymethyl cellulose and cytosine nucleoside is 1:3. After adding the inhibitor, let it react with the ore pulp one for 3 minutes. Then add 1200g of collector to each ton of titanium-rich phase ore powder one, and add diethyl phenylphosphonate and 3-chloro-o-anisidine to the flotation tank. And the mass ratio of diethyl phenylphosphonate and 3-chloro-o-anisidine is 1:4. After stirring for 1 minute, adjust the pH to 3; and let the added collector react with the ore pulp one for 4 minutes, then aerate the flotation tank for 1 minute and scrape the foam. After scraping the foam for 40 minutes, the foamed product is filtered and dried in turn to obtain titanium-rich phase ore powder two, and the ore pulp mixture remaining in the flotation tank is filtered and dried in turn to obtain titanium-poor phase ore powder two.

[0114] (7) Repeating the operations of step (5) and step (6) five times on the titanium-rich phase ore powder 2 after being selected and dried in step (6) to obtain titanium-rich phase ore powder 7 and titanium-poor phase ore powder 7. The recovery rate of titanium dioxide in the titanium-rich phase ore powder finally obtained is 64.16% and the grade of titanium dioxide is 46.43%.

[0115] Comparative Example 1

[0116] The ore sample used in Comparative Example 1 is the same as that in Example 7, and the extraction process is also the same as that in Example 7, except that no activator is added in Comparative Example 1.

[0117] Comparative Example 2

[0118] The ore sample selected in Comparative Example 2 is the same as that in Example 7, and the process for extracting titanium is also the same as that in Example 7, except that no inhibitor is added in Comparative Example 2.

[0119] Comparative Example 3

[0120] The ore sample selected in Comparative Example 3 is the same as that in Example 7, and the process for extracting titanium is also the same as that in Example 7, except that the collector in Comparative Example 3 is only diethyl phenylphosphonate.

[0121] Comparative Example 4

[0122] The ore sample selected in Comparative Example 4 is the same as that in Example 7, and the process for extracting titanium is also the same as that in Example 7, except that the inhibitor in Comparative Example 4 is only carboxymethyl cellulose.

[0123] Comparative Example 5

[0124] The ore sample selected in Comparative Example 5 is the same as that in Example 7, and the process for extracting titanium is also the same as that in Example 7, except that the number of selections in Comparative Example 5 is two.

[0125] Performance test experiment

[0126] In order to determine the performance of each product in multiple embodiments and multiple comparative examples of the present invention, the following performance test experiments were carried out respectively.

[0127] (1) Calculate the recovery rate Y of titanium dioxide in the titanium-rich phase ore powder finally obtained in each embodiment and each comparative example

[0128] The recovery rate can be calculated by the following formula: Wherein a is the amount of titanium dioxide in the vanadium-containing mineral to be extracted, and b is the amount of titanium dioxide in the final titanium-rich phase ore powder.

[0129] (2) The titanium dioxide grade W in the titanium-rich phase ore powder was measured by chemical titration. TiO2 .

[0130] The recovery rate Y of titanium dioxide and the grade W of titanium dioxide in the titanium-rich phase ore powder finally obtained in each embodiment and each comparative example are counted. TiO2 As shown in Table 1 below.

[0131] Table 1: Recovery rate Y of titanium dioxide and grade W of titanium dioxide in titanium-rich phase ore powder finally obtained in each embodiment and each comparative example TiO2

[0132] Recovery rate Y(%) <![CDATA[Grade W TiO2 (%)]]> Example 1 60.58 46.75 Example 2 61.53 47.59 Example 3 62.41 46.2 Example 4 60.63 47.71 Example 5 64.16 46.43 Example 6 64.93 48.15 Example 7 61.47 47.82 Comparative Example 1 64.13 32.2 Comparative Example 2 72.13 30.76 Comparative Example 3 63.73 28.28 Comparative Example 4 69.38 36.73 Comparative Example 5 72.46 38.87

[0133] Through the analysis of Examples 2 to 7, it can be seen that the recovery rates are all greater than 60% and the grade of titanium dioxide in the recovered titanium-rich phase ore powder is higher than 45%, reaching the grade standard of titanium concentrate (YB / T 4031-2015, the ferrous metallurgical industry standard of the People's Republic of China), which can prove that the method for extracting titanium from vanadium-containing minerals provided by the present invention can effectively recover titanium dioxide in vanadium-containing minerals, and the grade of titanium dioxide in the titanium-rich phase ore powder finally obtained after recovery is also very high, so that the titanium-rich phase ore powder finally obtained after recovery has high utilization value. Through the analysis of Examples 4 and 5, it can be seen that when the source of the extracted vanadium-containing minerals is vanadium slag after smelting in a vanadium-titanium magnetite blast furnace, adding different amounts of inhibitors and collectors will affect the recovery rate and grade of titanium dioxide in the titanium-rich phase ore powder finally extracted. Therefore, in the actual extraction process, the required recovery rate and grade of titanium-rich phase ore powder can be obtained by adjusting the amount of inhibitors and collectors added during the extraction process.

[0134] By analyzing Example 7 and Comparative Example 1, it can be seen that in the actual extraction process, not adding an activator will reduce the grade of titanium dioxide in the final product obtained by extraction, but the recovery rate of titanium dioxide in the final product will increase. Therefore, it is explained that adding the activator of this embodiment will reduce the recovery rate of titanium dioxide in the final product. It can be seen from this that if the grade of titanium dioxide in the final product obtained by extraction is not considered in the actual extraction process, the recovery rate of titanium dioxide in the final product can be improved by not adding an activator. If it is necessary to consider both the recovery rate of titanium dioxide and the grade of titanium dioxide in the final product obtained by extraction during the extraction process, it is necessary to add a certain amount of inhibitor, and the addition of an inhibitor can significantly improve the grade of titanium dioxide while slightly reducing the recovery rate of titanium dioxide.

[0135] By analyzing Example 7 and Comparative Example 2, it can be seen that in the actual extraction process, not adding an inhibitor will reduce the grade of titanium dioxide in the final product obtained by extraction, but the recovery rate of titanium dioxide in the final product will increase. Therefore, it is explained that adding the inhibitor of this embodiment will reduce the recovery rate of titanium dioxide in the final product. It can be seen from this that if the grade of titanium dioxide in the final product obtained by extraction is not considered in the actual extraction process, the recovery rate of titanium dioxide in the final product can be improved by not adding an inhibitor. If it is necessary to consider both the recovery rate of titanium dioxide and the grade of titanium dioxide in the final product obtained by extraction during the extraction process, it is necessary to add a certain amount of inhibitor. By adding an inhibitor, the grade of titanium dioxide can be significantly improved while slightly reducing the recovery rate of titanium dioxide.

[0136] By analyzing Example 7 and Comparative Example 3, it can be seen that in the actual extraction process, if only diethyl phenylphosphonate is added as a collector, it will also increase the recovery rate of titanium dioxide in the final product obtained by extraction, but will greatly reduce the grade of titanium dioxide in the final product obtained by extraction. This proves that diethyl phenylphosphonate and 3-chloro-o-anisidine have a synergistic effect and can simultaneously improve the grade of titanium dioxide in the final product obtained.

[0137] Through the analysis of Example 7 and Comparative Example 4, it can be seen that in the actual extraction process, if only carboxymethyl cellulose is added as an inhibitor, it will also reduce the grade of titanium dioxide in the final product obtained by extraction. It can be seen that by adding carboxymethyl cellulose and cytosine nucleoside at the same time, the grade of titanium dioxide in the final product obtained can be further improved. This proves that carboxymethyl cellulose and cytosine nucleoside have a synergistic effect and can simultaneously improve the grade of titanium dioxide in the final product obtained.

[0138] Through the analysis of Example 7 and Comparative Example 5, it can be seen that in the actual extraction process, as the number of selections increases, the recovery rate of titanium dioxide in the final product obtained by extraction will be lower. Because titanium dioxide is lost every time flotation is performed; a part of the titanium dioxide will enter the titanium-poor phase product after selection during the selection process, so as the number of selections increases, the recovery rate of titanium dioxide in the final product obtained by extraction will be lower. Therefore, in the actual extraction process, if the final extracted product needs to consider the grade and recovery rate of titanium dioxide at the same time, when extracting by this method, the number of selections should not be too many.

[0139] The above describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention to be protected. The scope of protection claimed by the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for separating and extracting valuable metal titanium from vanadium-containing minerals, characterized in that: It includes the following steps: S1: crushing the vanadium-containing mineral to obtain a mineral powder 1, and activating the mineral powder 1 with an activator; S2: filtering and drying the activated mineral powder 1 to obtain a mineral powder 2; adding water to the mineral powder 2 to form a slurry 1, adding a flotation agent to the slurry 1, adjusting the pH and stirring the slurry 1, and performing rough flotation on the slurry mixture 1 while stirring, to obtain a titanium-rich phase ore powder 1 and a titanium-poor phase ore powder 1 after rough flotation; S3: adding water to the titanium-rich phase ore powder 1 to form ore slurry 2, then adding the flotation agent to the ore slurry 2, adjusting the pH and stirring sufficiently, and performing fine flotation on the ore slurry mixture 2 while stirring, to obtain titanium-rich phase ore powder 2 and titanium-poor phase ore powder 2 after fine flotation; S4: Repeat step S3 multiple times, and finally obtain titanium-rich phase ore powder with a titanium dioxide grade higher than 45%; Wherein, the flotation agent comprises an inhibitor and a collector, the inhibitor comprises carboxymethyl cellulose and cytidine; the collector comprises diethyl phenylphosphonate and 3-chloro-o-anisidine; and the amount of the flotation agent added in step S3 is 80% of the amount of the flotation agent added in step S2.

2. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: The mass ratio of the inhibitor to the collector is 1:1 to 1:4; and / or The mass ratio of the carboxymethyl cellulose to the cytosine nucleoside is 1:2 to 1:4; and / or The mass ratio of the diethyl phenylphosphonate to the 3-chloro-o-anisidine is 1:1 to 1:

3.

3. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: The particle size range of the mineral powder obtained by the crushing process is 1μm to 74μm; and / or The concentration of the activator is 0.5 mol / L-1.5 mol / L, the activation time is 1 h-3 h, and the activation temperature is 40° C.-80° C.

4. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: The activator includes any one or a mixture of any two or more of sulfuric acid, sulfurous acid, sodium sulfate, copper sulfate, oxalic acid, lime, sulfur dioxide, lead nitrate, sodium carbonate, sodium hydroxide, lead salts, and barium salts; and / or The solid-liquid ratio of the activator to the mineral powder is 1:8 to 1:

15.

5. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: The pH range after adjustment in step S2 and step S3 is 1 to 6; the stirring time is 3 min to 5 min.

6. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: The mass percentage of the mineral powder 2 in the ore slurry 1 is 10% to 50%; the mass percentage of the titanium-rich phase mineral powder 1 in the ore slurry 2 is 10% to 50%.

7. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: The flotation time of the rough flotation and the fine flotation is 5 minutes to 60 minutes.

8. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In the step S2, the inhibitor is added in an amount of 500 g to 2000 g per ton of the mineral powder 2; the collector is added in an amount of 1000 g to 2000 g per ton of the mineral powder 2.

9. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: In the step S3, the inhibitor is added in an amount of 500 g to 2000 g per ton of the titanium-rich phase ore powder; the collector is added in an amount of 1000 g to 2000 g per ton of the titanium-rich phase ore powder.

10. The method for separating and extracting valuable metal titanium from vanadium-containing minerals according to claim 1, characterized in that: The vanadium-containing minerals include any one or a mixture of any two or more of the intermediates or tailings produced in the process of mining, smelting and sorting vanadium-titanium magnetite, the tailings produced by calcification, roasting and vanadium extraction of vanadium slag, and the tailings produced in the process of extracting vanadium from shale.

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