阅读说明：本技术 含钛钨原料酸解提钛提钨及含钛原料酸解提钛的方法 (Titanium-tungsten-containing raw material acidolysis titanium extraction and method for acidolysis titanium extraction of titanium-containing raw material ) 是由 边悟 鲁东 于 2019-03-14 设计创作，主要内容包括：本发明公开了一种含钛钨原料酸解提钛提钨及含钛原料酸解提钛的方法,属于冶金技术领域。本发明要解决的技术问题是提供一种能高效酸解含钛钨原料提钛提钨或含钛原料提钛的方法：将物料A、物料B和硫酸混合均匀进行反应,得反应物料C；将反应物料C与浸出剂混合,进行浸出,浸出完毕,固液分离即可。本发明显著提高了酸解率,缩短了酸解反应时间、浸出时间、钛液与尾渣分离时间,使废脱硝催化剂等难酸解的含钛钨原料也能实现经济可行的回收利用；并且可通过控制钒在偏钛酸与钛白废酸中的比例,生产钛钨复合产品、钒产品、钛钨钒复合产品等多种产品,应用范围广。(The invention discloses a method for extracting tungsten and titanium from a titanium-containing tungsten raw material through acidolysis, and belongs to the technical field of metallurgy. The invention aims to solve the technical problem of providing a method for extracting tungsten from a tungsten-containing raw material or titanium from a titanium-containing raw material by high-efficiency acidolysis, which comprises the following steps: uniformly mixing the material A, the material B and sulfuric acid for reaction to obtain a reaction material C; and mixing the reaction material C with a leaching agent, leaching, and performing solid-liquid separation after leaching. The method obviously improves the acidolysis rate, shortens the acidolysis reaction time, the leaching time and the separation time of the titanium liquid and the tailings, and ensures that titanium-containing tungsten raw materials which are difficult to be subjected to acidolysis, such as waste denitration catalysts and the like, can be economically and feasibly recycled; and various products such as titanium-tungsten composite products, vanadium products, titanium-tungsten-vanadium composite products and the like can be produced by controlling the proportion of vanadium in metatitanic acid and titanium white waste acid, and the application range is wide.)

1. The method for extracting tungsten from a titanium-containing tungsten raw material by acid hydrolysis and extracting titanium from the titanium-containing raw material by acid hydrolysis is characterized by comprising the following steps: the method comprises the following steps:

a. uniformly mixing the material A, the material B and sulfuric acid, and reacting to obtain a reaction material C; wherein the material A is at least one of a titanium-containing tungsten raw material or a titanium-containing raw material; the material B is at least one of a substance capable of carrying out dehydration reaction with sulfuric acid or a substance capable of carrying out dehydration reaction with sulfuric acid by hydrolysis under the action of sulfuric acid;

b. and mixing the reaction material C with a leaching agent, leaching, and after leaching, carrying out solid-liquid separation to obtain a titanium liquid and a filter cake.

2. The method for acid hydrolysis and titanium extraction of the raw material containing titanium and tungsten and the method for acid hydrolysis and titanium extraction of the raw material containing titanium as claimed in claim 1, wherein: in the step a, the mass ratio of tungsten trioxide to titanium dioxide in the material A is not less than 0 and not more than 50; preferably, the mass ratio of the tungsten trioxide to the titanium dioxide in the material A is more than or equal to 0 and less than or equal to 1.

3. The method for acid hydrolysis and titanium extraction of the raw material containing titanium and tungsten and the method for acid hydrolysis and titanium extraction of the raw material containing titanium as claimed in claim 1, wherein: in step a, at least one of the following is satisfied:

the mass ratio of the material B to the material A is 0.0001-10: 1;

preferably, the mass ratio of the material B to the material A is 0.01-0.3: 1;

h in the sulfuric acid₂SO₄The mass ratio of the material A to the material A is 0.5-5: 1;

preferably, H in the sulfuric acid₂SO₄The mass ratio of the material A to the material A is 1.3-1.7: 1.

4. the method for acid hydrolysis and titanium extraction of the raw material containing titanium and tungsten and the method for acid hydrolysis and titanium extraction of the raw material containing titanium as claimed in claim 1, wherein: in the step a, the mass concentration of the sulfuric acid is 10-100%, and the temperature is normal temperature-340 ℃; preferably, the mass concentration of the sulfuric acid is 85-98%, and the temperature is 200-240 ℃.

5. The method for acid hydrolysis and titanium extraction of the raw material containing titanium and tungsten and the method for acid hydrolysis and titanium extraction of the raw material containing titanium as claimed in claim 1, wherein: in the step a, the reaction temperature is 100-340 ℃, and the reaction time is 0.1-50 h; preferably, the reaction temperature is 200-240 ℃, and the reaction time is 0.5-2 h.

6. The method for acid hydrolysis and titanium extraction of the raw material containing titanium and tungsten and the method for acid hydrolysis and titanium extraction of the raw material containing titanium as claimed in claim 1, wherein: in the step b, the leaching agent is titanium white waste acid or sulfuric acid solution of 0-600 g/L; the dosage of the leaching agent is 1-200 times of the mass of the material A; preferably, the leaching agent is a sulfuric acid solution of 0 g/L-30 g/L; the dosage of the leaching agent is 2-5 times of the mass of the material A.

7. The method for acid hydrolysis and titanium extraction of the raw material containing titanium and tungsten and the method for acid hydrolysis and titanium extraction of the raw material containing titanium as claimed in claim 1, wherein: in step b, at least one of the following is satisfied:

the leaching temperature is not higher than 95 ℃;

and crushing the solidified materials in the reaction material C, and then leaching.

8. The method for acid hydrolysis and titanium extraction of the titanium-containing tungsten raw material and the method for acid hydrolysis and titanium extraction of the titanium-containing raw material as claimed in any one of claims 1 to 7, wherein: further comprising the steps of:

c. and c, hydrolyzing the titanium liquid obtained in the step b to obtain metatitanic acid slurry, and carrying out solid-liquid separation to obtain metatitanic acid filter cakes and titanium white waste acid.

9. The method for acid hydrolysis and titanium extraction of the raw material containing titanium and tungsten and the method for acid hydrolysis and titanium extraction of the raw material containing titanium as claimed in claim 8, wherein: one of the following is satisfied:

in the step c, after the titanium liquid is mixed with an oxidant, vanadium in the titanium liquid is partially or completely oxidized into pentavalent vanadium ions, and then hydrolysis is carried out;

in the step c, after the titanium solution is mixed with the reducing agent, vanadium in the titanium solution is partially or completely reduced into tetravalent and below vanadium ions, and then hydrolysis is carried out.

10. The method for acid hydrolysis and titanium extraction of the titanium-containing tungsten raw material and the method for acid hydrolysis and titanium extraction of the titanium-containing raw material as claimed in any one of claims 8 to 9, wherein: in the step c, the hydrolysis temperature is 95-150 ℃, and the hydrolysis time is 0.5-24 h. Preferably, the hydrolysis temperature is 95-106 ℃, and the hydrolysis time is 2-5 h.

Technical Field

The invention belongs to the technical field of metallurgy, and particularly relates to a method for extracting tungsten from a titanium-containing tungsten raw material through acidolysis and a method for extracting titanium from the titanium-containing raw material through acidolysis.

Background

Titanium ore is widely distributed in the earth crust and rock circles and in the stratum ten kilometers thick on the earth surface, the content of the titanium ore reaches six thousandths, and the titanium ore is relatively rich and is positioned in the tenth place of all elements. However, titanium is also considered to be a rare metal because it is extremely dispersed in nature and difficult to extract. Titanium has metallic luster, ductility and superconductivity. Titanium is mainly characterized by low density, high mechanical strength and easy processing. The plasticity of titanium depends primarily on purity, the more pure the titanium, the greater the plasticity. Has good corrosion resistance and is not influenced by atmosphere and seawater. At normal temperature, the corrosion of hydrochloric acid with the concentration below 7%, sulfuric acid with the concentration below 5%, nitric acid, aqua regia or dilute alkali solution is avoided; only hydrofluoric acid, concentrated hydrochloric acid, concentrated sulfuric acid, etc. can act on it. Titanium is an important alloying element in steels and alloys. The titanium compound is widely applied to the aspects of chemical industry, pigment, plastics, refractory materials, environmental protection, catalysis, electronics, aerospace and the like. It can be said that titanium is useful in every field known to us, and has a wide application prospect.

At present, the main raw materials for extracting titanium are: titanium ore, titanium slag, titanium-rich materials, titanium dioxide and the like. Many enterprises and scientific research institutes have made many studies on these titanium materials, resulting in a great amount of scientific research results. However, no major breakthrough is made in the aspect of utilization or regeneration of titanium-containing raw materials which are difficult to be subjected to acidolysis, such as waste SCR denitration catalysts.

CN201310315206.9 discloses a method for recovering titanium, vanadium, and tungsten from waste denitration catalyst, which adopts strong alkali to dissolve vanadium and tungsten in alkali solution and then extracts vanadium and tungsten respectively. Although the vanadium and tungsten are extracted by hot strong alkali, the method uses a large amount of high-temperature strong alkali to react with the vanadium and tungsten, so that the cost is too high and the economic benefit is general; meanwhile, a large amount of titanium dioxide treated by strong alkali is not recycled, so that secondary pollution is formed

CN201310642300.5 discloses a method for producing titanium solution by acidolysis: after sulfuric acid is mixed with titanium raw material, water is added to release heat to initiate acidolysis reaction, and the acidolysis rate reaches about 90%. If the method is used for acidolysis of the waste SCR denitration catalyst, even if the waste SCR denitration catalyst powder is added into concentrated sulfuric acid while stirring, the material can be hardened into blocks (possibly related to the generation of tungstic acid) and is tightly attached to a container, and the acidolysis rate is only about 30%; moreover, the leaching time is very long, and the separation of titanium liquid and tailings is also very difficult.

In the research on the influence factors of the acidolysis rate in titanium separation from the waste denitration catalyst published in modern chemical industry, billow, 2018 and the like, a method for acidolysis of the waste SCR denitration catalyst is disclosed: the acidolysis rate can be improved to 85 percent at 190 ℃ for 8h, and the concentration of the titanium solution reaches 180 g/L. The method needs high temperature reaction for 8 hours, the reaction time is too long, and the energy consumption and material consumption are too high; but also the problems of overlong leaching time and slow separation of titanium liquid and tailings caused by serious material hardening are still not solved; in addition, the hydrolysis control of each element in the hydrolysis of the tungsten-containing vanadium-titanium liquid prepared by the waste SCR denitration catalyst is not mentioned.

Disclosure of Invention

In order to solve the defects of extracting vanadium and tungsten in the prior art, the invention adopts the technical scheme that a method for extracting titanium and tungsten from a titanium-containing tungsten raw material through acidolysis and extracting titanium from a titanium-containing raw material through acidolysis is provided, wherein the method can improve the acidolysis rate of titanium, tungsten and vanadium, recycle titanium, tungsten and vanadium, and shorten the acidolysis reaction time, leaching time and separation time, and comprises the following steps:

a. uniformly mixing the material A, the material B and sulfuric acid, and reacting to obtain a reaction material C; wherein the material A is at least one of a titanium-containing tungsten raw material or a titanium-containing raw material; the material B is at least one of a substance capable of carrying out dehydration reaction with sulfuric acid or a substance capable of carrying out dehydration reaction with sulfuric acid by hydrolysis under the catalytic action of sulfuric acid;

b. and mixing the reaction material C with a leaching agent, leaching, and after leaching, carrying out solid-liquid separation to obtain a titanium liquid and a filter cake.

In the method for extracting tungsten from titanium-containing tungsten raw material through acidolysis and titanium extraction from titanium-containing raw material through acidolysis, in the step a, the mass ratio of tungsten trioxide to titanium dioxide in the material A is not less than 0 and not more than 50.

Preferably, in the method for extracting tungsten from titanium-containing tungsten raw material by acid hydrolysis and titanium from titanium-containing raw material by acid hydrolysis, in the step a, the mass ratio of tungsten trioxide to titanium dioxide in the material A is not less than 0 and not more than 1.

In the method for extracting tungsten from a titanium-containing tungsten raw material by acid hydrolysis and titanium from a titanium-containing raw material by acid hydrolysis, in the step a, the mass ratio of the material B to the material A is 0.0001-10: 1.

preferably, in the above method for extracting tungsten and titanium by acidolysis of a raw material containing titanium and tungsten and the method for extracting titanium by acidolysis of a raw material containing titanium and tungsten, in step a, the mass ratio of the material B to the material a is 0.01 to 0.3: 1.

wherein, in the method for extracting tungsten and titanium by acidolysis of the raw material containing titanium and tungsten and the method for extracting titanium by acidolysis of the raw material containing titanium, in the step a, H in the sulfuric acid₂SO₄The mass ratio of the material A to the material A is 0.5-5: 1.

preferably, in the above method for acid hydrolysis and extraction of tungsten and titanium from a raw material containing titanium and tungsten, in step a, H in the sulfuric acid₂SO₄The mass ratio of the material A to the material A is 1.3-1.7: 1.

in the method for extracting tungsten from a titanium-containing tungsten raw material through acidolysis and titanium extraction from a titanium-containing raw material through acidolysis, in the step a, the mass concentration of the sulfuric acid is 10-100%, and the temperature is normal temperature-340 ℃.

Preferably, in the above method for extracting tungsten and titanium by acid hydrolysis of a raw material containing titanium and tungsten and the method for extracting titanium by acid hydrolysis of a raw material containing titanium, in the step a, the mass concentration of the sulfuric acid is 85 to 98 percent, and the temperature is 200 to 240 ℃.

In the method for extracting tungsten from the titanium-containing tungsten raw material by acid hydrolysis and titanium from the titanium-containing raw material by acid hydrolysis, in the step a, the reaction temperature is 100-340 ℃ and the reaction time is 0.1-50 h.

Preferably, in the above method for extracting tungsten and titanium from a raw material containing titanium by acid hydrolysis, in step a, the reaction temperature is 200 to 240 ℃ and the reaction time is 0.5 to 2 hours.

In the method for extracting tungsten from a titanium-containing tungsten raw material through acidolysis and titanium from a titanium-containing raw material through acidolysis, in the step b, the leaching agent is titanium white waste acid or 0-600 g/L sulfuric acid solution.

Preferably, in the method for extracting tungsten from a titanium-containing tungsten raw material by acid hydrolysis and titanium from a titanium-containing raw material by acid hydrolysis, in the step b, the leaching agent is a sulfuric acid solution of 0g/L to 30 g/L.

In the method for extracting tungsten from a titanium-containing tungsten raw material through acidolysis and titanium extraction from a titanium-containing raw material through acidolysis, in the step b, the dosage of the leaching agent is 1-200 times of the mass of the material A.

Preferably, in the method for extracting tungsten from a titanium-containing tungsten raw material by acid hydrolysis and extracting titanium from a titanium-containing raw material by acid hydrolysis, in the step b, the dosage of the leaching agent is 2-5 times of the mass of the material A.

In the method for extracting tungsten from a titanium-containing tungsten raw material through acidolysis and titanium extraction from a titanium-containing raw material through acidolysis, in the step b, the leaching temperature is not higher than 95 ℃.

In the method for extracting tungsten from a titanium-containing tungsten raw material through acidolysis and titanium extraction from a titanium-containing raw material through acidolysis, in the step b, a solidified material in the reaction material C is crushed and then leached.

The method for extracting tungsten and titanium from the titanium-containing tungsten raw material through acidolysis comprises the following steps:

c. and c, hydrolyzing the titanium liquid obtained in the step b to obtain metatitanic acid slurry, and carrying out solid-liquid separation to obtain metatitanic acid filter cakes and titanium white waste acid.

In the above method for extracting tungsten from a titanium-containing tungsten raw material by acid hydrolysis and titanium from a titanium-containing raw material by acid hydrolysis, in step c, after mixing a titanium solution with an oxidant, vanadium in the titanium solution is partially or completely oxidized into pentavalent vanadium ions, and then hydrolysis is performed.

In the above method for extracting tungsten from a raw material containing titanium and tungsten by acid hydrolysis and titanium from a raw material containing titanium and tungsten by acid hydrolysis, in step c, after mixing the titanium solution with a reducing agent, vanadium in the titanium solution is partially or completely reduced to tetravalent or below vanadium ions, and then hydrolysis is performed.

In the method for extracting tungsten from the titanium-containing tungsten raw material by acid hydrolysis and titanium from the titanium-containing raw material by acid hydrolysis, in the step c, the hydrolysis temperature is 95-150 ℃ and the hydrolysis time is 0.5-24 h.

Preferably, the hydrolysis temperature is 95-106 ℃, and the hydrolysis time is 2-5 h.

The invention has the beneficial effects that:

the method is suitable for extracting tungsten and vanadium from the raw material containing titanium and tungsten and the raw material containing titanium, and can simultaneously carry out acidolysis on high added-value elements such as titanium, tungsten, vanadium and the like, particularly tungsten slightly soluble in sulfuric acid, so that the method is particularly suitable for the raw material containing titanium and tungsten, and particularly can improve the acidolysis rate of the raw material containing titanium and tungsten which is difficult to carry out acidolysis, such as a waste SCR denitration catalyst and the like. According to the method, the material B is added to react with sulfuric acid to form multi-bubble, and then the solidified crisp and expanded slurry enables the reaction materials to be easily stirred, dispersed more uniformly and contacted more fully, so that the hardening of the materials is avoided, the acidolysis reaction is remarkably promoted, and compared with the traditional process, the acidolysis rate, the leaching efficiency, the filtering efficiency and the like are greatly improved; and various products such as titanium-tungsten composite products, vanadium products, titanium-tungsten-vanadium composite products and the like can be produced by controlling the proportion of vanadium in metatitanic acid and titanium white waste acid, so that the application range is wide; the method is simple and easy to use, low in equipment requirement, convenient to operate, low in material consumption and energy consumption, easy to industrialize and good in economic benefit and social benefit.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

Specifically, the method for extracting tungsten from a titanium-containing tungsten raw material through acidolysis and extracting titanium from the titanium-containing raw material through acidolysis comprises the following steps:

a. uniformly mixing the material A, the material B and sulfuric acid, and reacting to obtain a reaction material C; wherein the material A is at least one of titanium-containing tungsten raw materials (such as waste denitration catalyst, titanium-tungsten composite titanium dioxide and the like) or titanium-containing (tungsten-free) raw materials (such as titanium ore, smelting titanium slag and the like); the material B is at least one of a substance capable of carrying out dehydration reaction with sulfuric acid or a substance capable of carrying out dehydration reaction with sulfuric acid by hydrolysis under the catalytic action of sulfuric acid;

b. and mixing the reaction material C with a leaching agent for leaching, and after leaching, carrying out solid-liquid separation to obtain titanium liquid and a carbon-containing tailings filter cake.

The method can perform acidolysis on various raw materials, wherein the mass ratio of tungsten trioxide to titanium dioxide in the material A is not less than 0 and not more than 50, preferably the mass ratio of tungsten trioxide to titanium dioxide in the material A is not less than 0 and not more than 1, and the titanium raw material is obtained when the mass ratio is 0.

The inventors have found unexpectedly in practice that: materials B (such as starch, cellulose, sugar, oil, meat, fat, ester, alcohol, carboxylic acid, phenol, ether, aldehyde, ketone, protein, amino acid, peptide, amine and other organic matters containing carbon and hydrogen oxygen and derivatives thereof) are dehydrated and release heat under the action of sulfuric acid, meanwhile, the materials B can generate reactions or phenomena such as gelatinization, expansion, gelation, crosslinking, thickening and the like to uniformly disperse the materials, certain B can be further dehydrated to generate carbon particles, the carbon is further oxidized to generate carbon dioxide, the sulfuric acid is reduced to generate sulfur dioxide and hydrogen sulfide, and generated gas can further uniformly disperse the materials and expand a reaction system; in addition, certain materials B (such as cellulose, starch, maltose, polysaccharide, ester, lipid, protein, peptide, ether, anhydride and derivatives thereof) can be hydrolyzed under the action of sulfuric acid, and the hydrolysate is subjected to the process of the first step, so that the system can be uniformly dispersed, and the acidolysis efficiency is improved. Therefore, in the method of the present invention, the material B contains a wide variety of substances, and the adopted functionality is defined as: at least one of a substance capable of undergoing a dehydration reaction with sulfuric acid or a substance capable of undergoing a dehydration reaction with sulfuric acid by hydrolysis under the catalytic action of sulfuric acid; preferably, the material B is a substance which can generate reactions or phenomena such as gelatinization, swelling, gelation, crosslinking, thickening and the like during batching or acidolysis so as to facilitate larger contact area, longer contact time, more uniform distribution and difficult sedimentation of reaction materials, and more preferably, the material B is a substance which contains very low elements besides carbon, hydrogen, oxygen, nitrogen, sulfur, silicon and iron.

In the step a of the method, the mass ratio of the material B to the material A is 0.0001-10: 1; in order to better exert the effect of the material B on the processes of acidolysis, separation and the like, preferably, the mass ratio of the material B to the material A is 0.01-0.3: 1.

in the step a of the method, the mass concentration of the sulfuric acid is 10-100%, and the temperature is normal temperature-340 ℃; the temperature of the material system and the high-concentration sulfuric acid are improved, so that the material B can participate in the reaction and the acidolysis speed can be improved, and the sulfuric acid can be preheated first, so that the acid before the material is solidified can be effectively utilizedThe time of the decomposition is preferably 85-98% by mass of the sulfuric acid, and the temperature is 200-240 ℃. In addition, because the material B is added, the dosage of the sulfuric acid needs to consider the acidolysis of the material A and the dehydration reaction of the material B at the same time, and experiments show that the H in the sulfuric acid is controlled₂SO₄The mass ratio of the material A to the material A is 0.5-5: 1, the reaction rate is favorably accelerated; preferably, H in sulfuric acid is controlled₂SO₄The mass ratio of the material A to the material A is 1.3-1.8: 1.

in the step a of the method, after materials are mixed, acidolysis reaction is started, and the process is as follows: the acidolysis is started when the materials are just mixed, and the reaction materials continue to accelerate the acidolysis in the uniformly dispersed organic matter material system along with the temperature rise; under the action of the material B, on one hand, the material is not easy to harden and is easy to stir; on the other hand, the generated gas can not overflow rapidly, so that the volume of the reaction system is increased continuously and can be increased to more than three times of the initial volume, the contact of reaction materials is more sufficient, and the acidolysis rate is improved; meanwhile, the volume ratio of the cured material is initially increased, a plurality of air holes are left, and the material is very brittle and beneficial to leaching; during acidolysis, tungsten oxide may react with sulfuric acid and titanium dioxide to generate a certain substance (tungsten oxide may coordinate with titanyl sulfate to form a certain complex), so that tungsten oxide can be dissolved in sulfuric acid solution, and tungsten extraction from tungsten-containing raw materials is facilitated. In conclusion, material B promotes the acidolysis of titanium, which in turn promotes the acidolysis of tungsten. In the step a, during the acidolysis reaction, the temperature is controlled to be 100-340 ℃, and the time is 0.1-50 h; the acidolysis reaction is preferably carried out at a temperature of 200 to 240 ℃ for 0.5 to 2 hours because the acidolysis reaction is facilitated by raising the reaction temperature.

In the step b of the method, the leaching agent is 0-600 g/L sulfuric acid solution (0g/L is water), and the leaching temperature is not higher than 95 ℃. In order to achieve the F value of common titanium liquid, the preferable leaching agent is 0 g/L-30 g/L sulfuric acid solution. The dosage of the leaching agent is 1-200 times of the mass of the acidolysis raw material; the dosage of the leaching agent generally requires that a large amount of titanium liquid is not hydrolyzed obviously to generate white suspended matters, so in order to accelerate the dissolution speed and prevent the leaching process from generating obvious hydrolysis reaction, the dosage of the leaching agent is preferably 2-5 times of the mass of the acidolysis raw materials.

The leaching end point is based on the standard that no solid material clings to a container, and because the material B is added, a curing system after acidolysis reaction contains a large number of air holes, the contact area of titanyl sulfate and a leaching agent is increased, after the titanyl sulfate is dissolved, the acidolysis tailings and the active carbon form an air hole framework collapse, and the leaching agent continues to destroy the next air hole; meanwhile, the curing system after acidolysis is very brittle, and if a crushing measure is added, the leaching speed is doubled, so that the leaching efficiency of the method is greatly improved compared with that of the traditional process (as in example 1).

After leaching, the activated carbon is uniformly dispersed in the acidolysis tailings to play roles in dispersing the tailings and increasing the void fraction, so that on one hand, the acidolysis tailings cannot be tightly combined together, and on the other hand, titanium liquid can easily pass through a filter cake during filtering, thereby increasing the filtering speed; therefore, the filtering speed of the method of the invention is greatly improved compared with the traditional process (as example 1).

In the step c of the method, the hydrolysis temperature is 95-150 ℃, and the hydrolysis time is 0.5-24 h. The preferable hydrolysis temperature is 95-106 ℃, and the hydrolysis time is 2-5 h.

The process of step c is as follows: hydrolyzing titanyl sulfate and water to generate metatitanic acid and sulfuric acid; after titanium titanyl sulfate combined with tungsten is hydrolyzed, tungsten is hydrolyzed along with the titanium (namely, when titanium liquid is hydrolyzed, tungsten is hydrolyzed, the condition that titanium is hydrolyzed and tungsten is not hydrolyzed does not exist); because these titanium tungsten materials or titanium materials often contain vanadium, which affects the quality of metatitanic acid, the vanadium content in metatitanic acid can be controlled by controlling the valence of vanadium according to the phenomena that tetravalent vanadium and vanadium below are hydrolyzed in a strong acid environment, and pentavalent vanadium is hydrolyzed into polyvanadate.

Therefore, in the step c of the method, the proportion of vanadium in the metatitanic acid and the titanium white waste acid can be controlled according to the requirement: 1. mixing the titanium liquid with an oxidant (hydrogen peroxide and the like), oxidizing part or all of vanadium into pentavalent vanadium ions, and hydrolyzing, wherein if the vanadium is basically pentavalent ions during hydrolysis, a large amount of vanadium enters metatitanic acid; 2. mixing the titanium liquid with a reducing agent (iron powder, hydrogen sulfide and the like), reducing vanadium partially or completely to tetravalent and below vanadium ions, and hydrolyzing, wherein if the vanadium in the titanium liquid is basically tetravalent or below vanadium ions during hydrolysis, the vanadium is basically in the titanium white waste acid and cannot be hydrolyzed into metatitanic acid. The vanadium content entering metatitanic acid by hydrolysis is different due to different oxidation degrees of vanadium, and the more pentavalent vanadium in the titanium solution, the more vanadium entering metatitanic acid; the less pentavalent vanadium, the less vanadium will enter metatitanic acid.

The method has the advantages that the material B is added, so that the tungstenic acid decomposition rate of titanium and tungstic acid can be improved, the energy consumption and the material consumption are reduced, the leaching time and the separation time are shortened, the amount of vanadium entering metatitanic acid can be controlled by controlling the valence state of the vanadium in the titanium liquid, and the problem of preparing a low-vanadium titanium white product from a high-vanadium titanium raw material is solved.

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

The titanium/tungsten-containing feedstock used in the examples had a particle size of-325 mesh and the chemical composition is shown in Table 1, and the stirring apparatus was a JJ-1 precision force-increasing electric stirrer.

TABLE 1 chemical composition/% of titanium/tungsten-containing feedstock

Name (R)	TiO2	WO3	TFe	CaO	MgO	SiO2	Al	P	V
										Waste denitration catalyst	87.21	4.99	0.05	0.98	0.05	3.13	0.421	0.04	0.448
Titanium-tungsten composite titanium dioxide	91.81	5.01	0.003			0.35		0.04	0.001
										Titanium ore	46.93		30.58	0.75	6.21	2.38	0.79	0.004	0.052
Smelting titanium slag	84.48		2.63	0.42	5.7	3.1	0.45	0.008	0.11
										Metatitanic acid	70.67		0.003						0.001
Anatase type titanium dioxide	98.55		0.004			0.15	0.10	0.05	0.001