A method for preparing titanium carbide / titanium oxide by carbothermally reducing a perovskite material

Abstract

A method for preparing titanium carbide / titanium oxide by carbon thermal reduction of perovskite material belongs to the technical field of metallurgical engineering and comprises the following steps: (1) grinding and sieving the perovskite material to obtain perovskite powder; (2) uniformly mixing the perovskite powder with carbon powder according to a certain ratio and then pressing into a block; (3) putting the formed block material into a high-temperature furnace for carbon thermal reduction reaction to obtain a carbonization product; and (4) crushing, separating and purifying the carbonization product, and then filtering and drying to obtain titanium carbide / titanium oxide powder. The above preparation method has the advantages of low raw material cost, simple process, high product added value, high titanium recovery rate and the like, and realizes the synergistic recovery of valuable elements in the perovskite material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metallurgical engineering, and particularly relates to a method for preparing titanium carbide / titanium oxycarbide from carbon thermal reduction of perovskite materials. BACKGROUND

[0002] Titanium carbide (TiC) is a transition metal carbide, which has a NaCl type face-centered cubic crystal structure, and coexists with covalent bonds, ionic bonds and metallic bonds. The special structure of titanium carbide determines that it has characteristics such as wear resistance, high hardness, high melting point, stable chemical properties and excellent electrical conductivity and thermal conductivity, and is a very valuable material, which is widely used in aerospace, mechanical processing, electronic industry and other fields. Titanium carbide has good wettability with some metals, and can be used as an important reinforcing phase of metal-based composite ceramics to improve the physical and chemical properties of the material. When nano-titanium carbide powder is added to hard alloy as a dispersion phase, with the continuous reduction of the particle size of titanium carbide powder, the alloy can be reinforced and toughened under the action of size effect. At present, the methods for preparing titanium carbide include direct reaction method, TiO2 carbon thermal reduction method, metal thermal reduction method, gas phase reaction synthesis method and microwave synthesis method. In industry, carbon thermal reduction method is used to obtain titanium carbide by reducing titanium dioxide and carbon black at high temperature, which has the advantage of simple process, but the price of titanium dioxide is relatively high, so it is necessary to explore a low-cost preparation method. In the process of preparing titanium carbide by carbon thermal reduction of titanium dioxide, a continuous solid solution transition phase titanium oxycarbide (TiC x O 1-x ) is produced. It can be considered that part of the carbon atoms in the titanium carbide lattice are replaced by oxygen atoms. This substance is similar to titanium carbide in structure and properties, has good electrical conductivity and chemical stability, and has been successfully applied in the electrolytic preparation of titanium metal by soluble anode, and is also a very promising material.

[0003] Most existing titanium carbide synthesis processes use expensive high-purity titanium sources such as titanium dioxide and metallic titanium as reactants, resulting in low economic efficiency. Perovskite, a titanium-containing material with broad application prospects, is a promising alternative for finding inexpensive raw materials. Perovskite can be divided into natural and synthetic perovskite. In the 19th century, German mineralogist Gustav Rose first discovered natural perovskite, naming it "Perovskite" in honor of Russian geologist Lev Perovski. Natural perovskite often contains small amounts of other minerals, leading to low utilization rates. Synthetic perovskite, due to its higher purity, has significant application value. Patents CN103343174A and CN106048108A disclose methods for enriching titanium elements and obtaining perovskite concentrate by melting and oxidizing titanium-containing slag. After processing with the above technology, a large amount of synthetic perovskite concentrate with a TiO2 grade of over 30% can be obtained from titanium-containing slag. Further research is needed on how to further utilize perovskite. Currently, the application of perovskite is limited to the production of titanium dioxide using the sulfuric acid process. However, the production of titanium dioxide often results in problems such as pipeline blockage caused by calcium sulfate and the accumulation of large amounts of byproducts. The lack of efficient resource utilization methods hinders the application and development of perovskite.

[0004] Based on the current applications of perovskite, the in-situ carbothermal reduction method using perovskite as a titanium source can achieve low-cost and high-efficiency preparation of titanium carbide / titanium oxide. The synthesis of titanium carbide / titanium oxide, in turn, provides a new approach for the utilization of perovskite. Summary of the Invention

[0005] To address the problems of high production costs and low utilization efficiency of perovskite in existing technologies for titanium carbide / titanium oxide, this invention provides a method for preparing titanium carbide / titanium oxide from carbothermic perovskite materials. This method effectively utilizes perovskite materials while achieving low-cost preparation of titanium carbide / titanium oxide.

[0006] A method for preparing titanium carbide / titanium oxide from carbothermic reduction perovskite minerals includes the following steps:

[0007] (1) Grind and sieve the perovskite material to obtain perovskite powder;

[0008] (2) Mix perovskite powder and carbon powder evenly at a mass ratio of 10:1 to 7, and then press them into blocks;

[0009] (3) Place the formed block material in a graphite crucible and heat it in a high-temperature furnace to carry out a carbothermic reduction reaction to obtain carbonized products. The reduction time is 2 to 8 hours. The reaction system is kept in a vacuum state or argon is introduced as a protective atmosphere.

[0010] The carbothermic reduction reaction is one of the following:

[0011] When the spinel phase exists in the perovskite material, the corresponding case A, case B or case C;

[0012] Case A: the carbonization product is titanium carbide / carbon titanium oxide, calcium aluminate and magnesium vapor when the reaction temperature is controlled at 1100-1300℃ under the vacuum degree of 1-100Pa;

[0013] Case B: the carbonization product is titanium carbide / carbon titanium oxide, calcium aluminate and magnesium oxide when the reaction temperature is controlled at 1400-1800℃ under the argon atmosphere;

[0014] Case C: the carbonization product is titanium carbide / carbon titanium oxide, calcium carbide, calcium aluminate and magnesium vapor when the reaction temperature is controlled at 1850-2000℃ under the argon atmosphere;

[0015] When the spinel phase does not exist in the perovskite material, the corresponding case D, case E or case F;

[0016] Case D: the carbonization product is titanium carbide / carbon titanium oxide and calcium oxide when the reaction temperature is controlled at 1100-1300℃ under the vacuum degree of 1-100Pa;

[0017] Case E: the carbonization product is titanium carbide / carbon titanium oxide and calcium oxide when the reaction temperature is controlled at 1400-1800℃ under the argon atmosphere;

[0018] Case F: the carbonization product is titanium carbide / carbon titanium oxide and calcium carbide when the reaction temperature is controlled at 1850-2000℃ under the argon atmosphere;

[0019] (4) crushing the carbonization product, separating and purifying the crushed material, and then filtering and drying to obtain the titanium carbide / carbon titanium oxide powder;

[0020] The separation and purification method is as follows:

[0021] When the carbothermic reduction reaction is case A or case B, method one, method two, method three or method four is adopted;

[0022] When the carbothermic reduction reaction is case C, method five is adopted;

[0023] When the carbothermic reduction reaction is case D or case E, method six or method seven is adopted;

[0024] When the carbothermic reduction reaction is case F, method eight is adopted;

[0025] Method one: impurity removal by acid leaching, the carbonization product is added into 4-9mol / L hydrochloric acid solution for leaching to obtain titanium carbide / carbon titanium oxide and leaching solution, and the calcium and aluminum components can be separated from the leaching solution by subsequent hydrometallurgy;

[0026] Method two: acid leaching after magnetic separation, first, the carbonized product is separated by magnetic separation, then the concentrate after magnetic separation is purified by 0.5-2 mol / L hydrochloric acid solution to obtain titanium carbide / carbon titanium oxide, and the main component of the tailings of magnetic separation is calcium aluminate, which can be used as cement raw material and building material;

[0027] Method three: acid leaching after alkali leaching, first, the carbonized product is added to sodium hydroxide solution and leached at 80-120℃ to obtain leaching residue and sodium aluminate solution, then the leaching residue is added to hydrochloric acid solution and leached at 50-90℃ to obtain titanium carbide / carbon titanium oxide and leaching solution, and the main component of the leaching solution is calcium chloride solution;

[0028] Method four: alkali leaching, magnetic separation and acid leaching, the carbonized product is added to a mixed solution of sodium carbonate-sodium hydroxide and leached at 160-200℃ to obtain leaching residue and sodium aluminate solution, then the leaching residue is separated by magnetic separation, and the concentrate of magnetic separation is purified by 0.5-2 mol / L hydrochloric acid solution to obtain titanium carbide / carbon titanium oxide, and the main component of the tailings of magnetic separation is calcium carbonate, which can be used as building material;

[0029] Method five: acid leaching, the carbonized product is added to 4-9 mol / L hydrochloric acid solution for leaching to obtain titanium carbide / carbon titanium oxide, leaching solution and acetylene, and the calcium and aluminum components can be separated by subsequent hydrometallurgy;

[0030] Method six: acid leaching, the carbonized product is added to hydrochloric acid solution and leached at 50-90℃ to obtain titanium carbide / carbon titanium oxide and calcium chloride solution;

[0031] Method seven: water leaching, magnetic separation and acid leaching, the carbonized product is added to deionized water to obtain water leaching material, then the water leaching material is separated by magnetic separation, and the concentrate of magnetic separation is purified by 0.5-2 mol / L hydrochloric acid solution to obtain titanium carbide / carbon titanium oxide, and the main component of the tailings of magnetic separation is calcium hydroxide, which can be used as building material;

[0032] Method eight: water leaching, magnetic separation and acid leaching, the carbonized product is added to deionized water to obtain water leaching material and acetylene, then the water leaching material is separated by magnetic separation, and the concentrate of magnetic separation is purified by 0.5-2 mol / L hydrochloric acid solution to obtain titanium carbide / carbon titanium oxide, and the main component of the tailings of magnetic separation is calcium hydroxide, which can be used as building material.

[0033] The above method for preparing titanium carbide / carbon titanium oxide from carbothermic reduction of perovskite material, wherein:

[0034] The titanium carbide / carbon titanium oxide is one of titanium carbide, carbon titanium oxide or a mixture thereof.

[0035] The perovskite material in step (1) is perovskite concentrate or perovskite concentrate, and the main crystal phase is perovskite, and there is or is not magnesium-aluminum spinel phase, wherein the content of TiO2 is 30-60%.

[0036] The particle size of the perovskite powder obtained in step (1) is ≤74 μm.

[0037] The carbon powder in step (2) is one of carbon black, graphite, activated carbon, petroleum coke, anthracite, coal powder and coke.

[0038] The particle size of the crushed material in step (4) is ≤74 μm.

[0039] The acid leaching temperature of method one, method two, method four, method five, method seven and method eight in step (4) is 50-90℃, the liquid-solid ratio is 3-7:1, and the leaching time is 30-60min.

[0040] The concentration of sodium hydroxide in method three in step (4) is 1-3 mol / L, the liquid-solid ratio is 3-5:1, the leaching time is 30-60min, the concentration of hydrochloric acid is 2-6 mol / L, the liquid-solid ratio is 3-5:1, and the leaching time is 30-60min.

[0041] The concentration of sodium carbonate in the mixed solution of sodium carbonate-sodium hydroxide in method four in step (4) is 1-6 mol / L, the concentration of sodium hydroxide is 1-3 mol / L, the liquid-solid ratio is 3-5:1, and the leaching time is 60-120min.

[0042] The concentration of hydrochloric acid in method six in step (4) is 3-6 mol / L, the liquid-solid ratio is 3-5:1, and the leaching time is 30-60min.

[0043] The beneficial effects of the present application are:

[0044] 1. The present application uses perovskite material with low titanium dioxide content as raw material, and in-situ synthesizes titanium carbide / carbon titanium oxide powder by carbon thermal reduction method, the price of raw material is low, the preparation process is simple, the recovery rate of titanium is high, and the economic benefit is remarkable.

[0045] 2. The content of Fe, Si and other impurities in the raw material used in the present application is very low, which creates favorable conditions for subsequent separation of titanium components, and at the same time, a purification scheme suitable for a wide range of applications and friendly to the environment is proposed for the separation of titanium carbide / carbon titanium oxide products and impurity components, the purification method is simple and efficient, the acid and alkali consumption is small, and the requirements for equipment and experimental conditions are relatively mild.

[0046] 3. The titanium carbide / carbon titanium oxide product obtained by the present application has high purity, the by-products in the preparation process can be used subsequently, the titanium, calcium, aluminum and other elements in the perovskite material are recycled, and high value-added products are obtained.

[0047] 4. In the study of the behavior of carbonthermal reduction of perovskite material, it is found that the occurrence state of titanium element can be changed from perovskite to titanium carbide through carbonthermal reduction reaction, and titanium oxide can appear in part of the carbonized product, the production mechanism of which is that oxygen atoms in titanium carbide lattice occupy part of the carbon atom sites, which can be considered that oxygen atoms doped in titanium carbide crystal in the form of isomorphism, thereby forming the intermediate product titanium oxide solid solution of carbonthermal reduction reaction. Titanium oxide and titanium carbide have similar crystal structure and properties, both of which have excellent characteristics such as high hardness, high melting point, good electrical conductivity and thermal conductivity, etc. In the present application, the composition of titanium carbide / titanium oxide product can be controlled by controlling the carbon content of the reaction system, reaction time and other process parameters. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 Figure 1 is a flowchart of the method for preparing titanium carbide / titanium oxide by carbonthermal reduction of perovskite material in Example 1 of the present application;

[0049] Figure 2 Figure 2 is an XRD pattern of the perovskite material used in Example 1 of the present application;

[0050] Figure 3 Figure 3 is an XRD pattern of the titanium carbide powder obtained in Example 1 of the present application;

[0051] Figure 4 Figure 4 is a flowchart of the method for preparing titanium carbide / titanium oxide by carbonthermal reduction of perovskite material in Example 2 of the present application;

[0052] Figure 5 Figure 5 is a flowchart of the method for preparing titanium carbide / titanium oxide by carbonthermal reduction of perovskite material in Example 3 of the present application;

[0053] Figure 6 Figure 6 is a flowchart of the method for preparing titanium carbide / titanium oxide by carbonthermal reduction of perovskite material in Example 4 of the present application;

[0054] Figure 7 Figure 7 is a flowchart of the method for preparing titanium carbide / titanium oxide by carbonthermal reduction of perovskite material in Example 5 of the present application. DETAILED DESCRIPTION

[0055] The present application will be further described below in conjunction with the examples:

[0056] The perovskite material used in Example 1, Example 2 and Example 3 of the present application mainly contains perovskite (CaTiO3) and magnesium aluminum spinel (MgAl2O4), the components and contents of which are shown in Table 1; the perovskite material used in Example 4 and Example 5 of the present application mainly contains perovskite (CaTiO3), the components and contents of which are shown in Table 2.

[0057] Table 1 Chemical composition and content (wt.%) of perovskite material used in Example 1, Example 2, Example 3

[0058]

[0059] Table 2 Chemical composition and content (wt.%) of perovskite material used in Example 4, Example 5

[0060]

[0061] Example 1

[0062] A method for preparing titanium carbide by carbothermic reduction of perovskite material, as shown in Figure 1 , the operation steps are as follows:

[0063] (1) The perovskite material is ground and sieved to obtain perovskite powder with a particle size of ≤74 μm;

[0064] (2) The perovskite powder and carbon black powder are mixed uniformly in a mass ratio of 10:2.5 in a ball mill, and then pressed into a block;

[0065] (3) The formed block material is placed in a graphite crucible and put into a high-temperature furnace to heat to 1250℃ for carbothermic reduction reaction, the reduction time is 4h, and the vacuum degree in the furnace is maintained at 30Pa during the reaction, to obtain carbonization products of titanium carbide, calcium aluminate and magnesium vapor;

[0066] (4) The carbonization products are crushed to have a particle size of ≤74 μm, and first subjected to magnetic separation, and then the concentrate after magnetic separation is purified with 1 mol / L hydrochloric acid solution, the leaching temperature is 60℃, the liquid-solid ratio is 5:1, the leaching time is 30min, and after filtration and drying, titanium carbide powder is obtained, and the tailings after magnetic separation mainly contain calcium aluminate, which can be used as a cement raw material and a building material.

[0067] The perovskite material and the final product used in this embodiment are subjected to phase analysis, and the detection results are shown in Figure 2 and Figure 3 , from which it can be seen that the perovskite material is composed of perovskite and magnesium aluminate spinel, and the final product is titanium carbide.

[0068] Example 2

[0069] A method for preparing titanium carbide by carbothermic reduction of perovskite material, as shown in Figure 4 , the operation steps are as follows:

[0070] (1) The perovskite material is ground and sieved to obtain perovskite powder with a particle size of ≤74 μm;

[0071] (2) The perovskite powder and graphite powder are mixed uniformly in a ball mill at a mass ratio of 10:2.2, and then pressed into a block;

[0072] (3) The shaped block material is placed in a graphite crucible and put into a high-temperature furnace to be heated to 1550°C for carbonthermal reduction reaction, the reduction time is 6h, argon is introduced into the reaction system as a protective atmosphere, and carbonized products titanium carbide, calcium aluminate and magnesium oxide are obtained;

[0073] (4) The carbonized products are crushed to have a particle size of ≤74μm, then the carbonized products are added into a 6mol / L hydrochloric acid solution to leach at 80°C for 60min, the liquid-solid ratio is 5:1, after filtration, solid substances and leaching solution are obtained, the solid substances are dried to obtain titanium carbide powder, and the leaching solution can separate calcium and aluminum components through subsequent hydrometallurgy.

[0074] Example 3

[0075] A method for preparing titanium oxycarbide by carbonthermal reduction of perovskite material is shown in Figure 5 , and the operation steps are as follows:

[0076] (1) The perovskite material is ground and sieved to obtain perovskite powder with a particle size of ≤74μm;

[0077] (2) The perovskite powder and activated carbon powder are mixed uniformly in a ball mill at a mass ratio of 10:1.9, and then pressed into a block;

[0078] (3) The shaped block material is placed in a graphite crucible and put into a high-temperature furnace to be heated to 1450°C for carbonthermal reduction reaction, the reduction time is 4h, argon is introduced into the reaction system as a protective atmosphere, and carbonized products titanium oxycarbide, calcium aluminate and magnesium oxide are obtained;

[0079] (4) The carbonized products are crushed to have a particle size of ≤74μm, then the carbonized products are added into a mixed solution of 3mol / L sodium carbonate and 2mol / L sodium hydroxide to leach at 180°C for 90min, the liquid-solid ratio is 4:1, leaching residue and sodium aluminate solution are obtained, then the leaching residue is separated by magnetic separation, the magnetic separation concentrate is purified by using 1mol / L hydrochloric acid solution, the leaching temperature is 60°C, the liquid-solid ratio is 5:1, the leaching time is 30min, after filtration and drying, titanium oxycarbide powder is obtained, and the main component of the magnetic separation tailings is calcium carbonate, which can be used as a building material.

[0080] Example 4

[0081] A method for preparing titanium oxycarbide by carbonthermal reduction of perovskite material is shown in Figure 6 , and the operation steps are as follows:

[0082] (1) The perovskite material is ground and sieved to obtain perovskite powder with a particle size of ≤74μm;

[0083] (2) The perovskite powder and graphite powder are mixed in a ball mill at a mass ratio of 10:2.2, and then pressed into a block;

[0084] (3) The formed block material is placed in a graphite crucible and put into a high-temperature furnace to be heated to 1500°C for carbonthermal reduction reaction, the reduction time is 4h, argon gas is introduced into the reaction system as a protective atmosphere, and the carbonized product titanium carbide and calcium oxide are obtained;

[0085] (4) The carbonized product is crushed to a particle size of ≤74μm, then the carbonized product is added to a 4mol / L hydrochloric acid solution and leached at 60°C for 40min, the liquid-solid ratio is 5:1, after filtration, solid material and calcium chloride solution are obtained, and the solid material is dried to obtain titanium carbide powder.

[0086] Example 5

[0087] A method for preparing titanium carbide by carbonthermal reduction of perovskite material, as shown in Figure 7 , the operation steps are as follows:

[0088] (1) The perovskite material is ground and sieved to obtain perovskite powder with a particle size of ≤74μm;

[0089] (2) The perovskite powder and carbon black powder are mixed in a ball mill at a mass ratio of 10:5.5, and then pressed into a block;

[0090] (3) The formed block material is placed in a graphite crucible and put into a high-temperature furnace to be heated to 1900°C for carbonthermal reduction reaction, the reduction time is 4h, argon gas is introduced into the reaction system as a protective atmosphere, and the carbonized product titanium carbide and calcium carbide are obtained;

[0091] (4) The carbonized product is crushed to a particle size of ≤74μm, the crushed material is added to deionized water to obtain water leaching material and acetylene, then the water leaching material is separated by magnetic separation, the magnetic separation concentrate is purified with 1mol / L hydrochloric acid, the leaching temperature is 60°C, the liquid-solid ratio is 5:1, the leaching time is 30min, after filtration and drying, titanium carbide powder is obtained, and the main component of the magnetic separation tailings is calcium hydroxide, which can be used as a building material.

Claims

1. A method for producing titanium carbide / titanium oxide by carbothermic reduction of a perovskite material, characterized in that, The method comprises the following steps: (1) grinding and screening the perovskite material to obtain perovskite powder; (2) uniformly mixing the perovskite powder with carbon powder at a mass ratio of 10:1~7, and then pressing into a block; (3) placing the formed block material in a graphite crucible and placing it in a high-temperature furnace for heating to perform a carbothermic reduction reaction to obtain a carbonized product, the reduction time being 2~8 h, and the reaction system being kept in a vacuum state or being supplied with argon as a protective atmosphere; wherein the carbothermic reduction reaction is one of the following cases: when the perovskite material contains a magnesium-aluminum spinel phase, the corresponding case is case A, case B or case C; case A: the reaction temperature is controlled at 1100~1300℃ under a vacuum degree of 1~100 Pa, and the carbonized product obtained is titanium carbide / carbon titanium oxide, calcium aluminate and magnesium vapor; case B: the reaction temperature is controlled at 1400~1800℃ under the condition of supplying argon, and the carbonized product obtained is titanium carbide / carbon titanium oxide, calcium aluminate and magnesium oxide; case C: the reaction temperature is controlled at 1850~2000℃ under the condition of supplying argon, and the carbonized product obtained is titanium carbide / carbon titanium oxide, calcium carbide, calcium aluminate and magnesium vapor; when the perovskite material does not contain a magnesium-aluminum spinel phase, the corresponding case is case D, case E or case F; case D: the reaction temperature is controlled at 1100~1300℃ under a vacuum degree of 1~100 Pa, and the carbonized product obtained is titanium carbide / carbon titanium oxide and calcium oxide; case E: the reaction temperature is controlled at 1400~1800℃ under the condition of supplying argon, and the carbonized product obtained is titanium carbide / carbon titanium oxide and calcium oxide; case F: the reaction temperature is controlled at 1850~2000℃ under the condition of supplying argon, and the carbonized product obtained is titanium carbide / carbon titanium oxide and calcium carbide; (4) crushing the carbonized product, separating and purifying the crushed material, and then filtering and drying to obtain titanium carbide / carbon titanium oxide powder; the titanium carbide / carbon titanium oxide is one of titanium carbide and carbon titanium oxide or a mixture thereof; the separation and purification method is: when the carbothermic reduction reaction is case A or case B, method one, method two, method three or method four is adopted; when the carbothermic reduction reaction is case C, method five is adopted; when the carbothermic reduction reaction is case D or case E, method six or method seven is adopted; when the carbothermic reduction reaction is case F, method eight is adopted; method one: acid leaching for impurity removal, the carbonized product is added into a 4~9 mol / L hydrochloric acid solution for leaching, titanium carbide / carbon titanium oxide and a leaching solution are obtained, and the calcium and aluminum components are separated from the leaching solution by subsequent hydrometallurgy; method two: magnetic separation followed by acid leaching for impurity removal, the carbonized product is first subjected to magnetic separation, and then the concentrate after magnetic separation is purified with a 0.5~2 mol / L hydrochloric acid solution to obtain titanium carbide / carbon titanium oxide, and the tailings after magnetic separation mainly contain calcium aluminate, which can be used as a cement raw material or a building material; method three: alkali leaching followed by acid leaching for impurity removal, the carbonized product is first added into a sodium hydroxide solution and subjected to leaching at 80~120℃ to obtain leaching residue and a sodium aluminate solution, and then the leaching residue is added into a hydrochloric acid solution and subjected to leaching at 50~90℃ to obtain titanium carbide / carbon titanium oxide and a leaching solution, and the main component of the leaching solution is a calcium chloride solution; Method four: after alkaline leaching and magnetic separation, acid leaching, the carbonized product is added into a mixed solution of sodium carbonate and sodium hydroxide, and leaching is carried out at 160-200℃, to obtain leaching residue and sodium aluminate solution, then the leaching residue is separated by magnetic separation, and the concentrate is purified by 0.5-2 mol / L hydrochloric acid solution to obtain titanium carbide / titanium oxycarbide, and the tailings mainly contain calcium carbonate and are used as building materials; Method five: after acid leaching, the carbonized product is added into 4-9 mol / L hydrochloric acid solution for leaching, to obtain titanium carbide / titanium oxycarbide, leaching solution and acetylene, and the calcium and aluminum components are separated by subsequent hydrometallurgy; Method six: after acid leaching, the carbonized product is added into hydrochloric acid solution for leaching at 50-90℃, to obtain titanium carbide / titanium oxycarbide and calcium chloride solution; Method seven: after water leaching and magnetic separation, acid leaching, the carbonized product is added into deionized water to obtain water leaching material, then the water leaching material is separated by magnetic separation, and the concentrate is purified by 0.5-2 mol / L hydrochloric acid solution to obtain titanium carbide / titanium oxycarbide, and the tailings mainly contain calcium hydroxide and are used as building materials; Method eight: after water leaching and magnetic separation, acid leaching, the carbonized product is added into deionized water to obtain water leaching material and acetylene, then the water leaching material is separated by magnetic separation, and the concentrate is purified by 0.5-2 mol / L hydrochloric acid solution to obtain titanium carbide / titanium oxycarbide, and the tailings mainly contain calcium hydroxide and are used as building materials.

2. A process for the carbothermic reduction of a perovskite material to produce titanium carbide / titanium oxide according to claim 1, characterised in that, The perovskite material in step (1) is perovskite concentrate or perovskite middling, and the main crystal phase is perovskite, and there is or is not magnesium-aluminum spinel phase, wherein the content of TiO2 is 30-60%.

3. A process for the carbothermic reduction of a perovskite material to produce titanium carbide / titanium oxide according to claim 1, characterised in that, The particle size of the perovskite powder obtained in step (1) is ≤74 μm.

4. The method of producing titanium carbide / titanium oxide by carbothermic reduction of a perovskite material according to claim 1, characterized in that, The carbon powder in step (2) is one of carbon black, graphite, activated carbon, petroleum coke, anthracite, coal powder and coke.

5. The method of producing titanium carbide / titanium oxide by carbothermic reduction of a perovskite material according to claim 1, characterized in that, The particle size of the crushed material in step (4) is ≤74 μm.

6. The method of producing titanium carbide / titanium oxide by carbothermic reduction of a perovskite material according to claim 1, characterized in that, In method one, method two, method four, method five, method seven and method eight in step (4), the acid leaching temperature is 50-90℃, the liquid-solid ratio is 3-7:1, and the leaching time is 30-60 min.

7. A process for the carbothermic reduction of a perovskite material to produce titanium carbide / titanium oxide according to claim 1, characterised in that, In method three in step (4), the concentration of sodium hydroxide solution is 1-3 mol / L, the liquid-solid ratio is 3-5:1, the leaching time in sodium hydroxide solution is 30-60 min, the concentration of hydrochloric acid solution is 2-6 mol / L, the liquid-solid ratio is 3-5:1, and the leaching time in hydrochloric acid solution is 30-60 min.

8. The method of producing titanium carbide / titanium oxide by carbothermic reduction of a perovskite material according to claim 1, characterized in that, In method four in step (4), the concentration of sodium carbonate in the mixed solution of sodium carbonate and sodium hydroxide is 1-6 mol / L, the concentration of sodium hydroxide is 1-3 mol / L, the liquid-solid ratio is 3-5:1, and the leaching time is 60-120 min.

9. The method of producing titanium carbide / titanium oxide by carbothermic reduction of a perovskite material according to claim 1, characterized in that, In method six in step (4), the concentration of hydrochloric acid solution is 3-6 mol / L, the liquid-solid ratio is 3-5:1, and the leaching time is 30-60 min.

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