阅读说明：本技术 一种钒钛磁铁矿钒钛资源综合利用的方法 (Method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite ) 是由 朱庆山 杨海涛 范川林 李洪钟 于 2019-10-25 设计创作，主要内容包括：本发明属于化工、冶金领域。具体地,本发明公开了一种钒钛磁铁矿钒钛资源综合利用的方法。通过将吹钒工序得到的钒渣返回电炉熔分工序,使钒从钛渣开路,改变钒的提取路径,实现钒钛共提,彻底解决了提钒尾渣处理难题。通过控制含钒钛渣破碎粒径,配加细粒碳粉、粘结剂造粒,强化矿/碳接触,并耦合催化氯化,降低氯化反应温度,解决高钙镁钛资源的利用难题。通过四氯化钛除钒干渣配加还原剂和钢屑直接冶炼钒铁合金,从而省略了五氧化二钒中间品的制备,大大缩短流程,降低生产成本。本方法可实现钒钛磁铁矿中钒钛资源的综合利用,分别得到四氯化钛和钒铁合金产品,具有资源利用率高,节能降耗,环境友好,产品附加值高等优点。(The invention belongs to the field of chemical industry and metallurgy. Specifically, the invention discloses a method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite. The vanadium slag obtained in the vanadium blowing process is returned to the electric furnace melting process, so that the vanadium is separated from the titanium slag, the extraction path of the vanadium is changed, the vanadium and titanium are extracted together, and the problem of treatment of vanadium extraction tailings is thoroughly solved. The crushing particle size of the vanadium-containing titanium slag is controlled, fine carbon powder and a binder are added for granulation, ore/carbon contact is strengthened, catalytic chlorination is coupled, chlorination reaction temperature is reduced, and the problem of utilization of high-calcium magnesium titanium resources is solved. The vanadium ferrovanadium alloy is directly smelted by adding the reducing agent and the steel scrap into the titanium tetrachloride vanadium-removing dry slag, so that the preparation of a vanadium pentoxide intermediate product is omitted, the flow is greatly shortened, and the production cost is reduced. The method can realize the comprehensive utilization of vanadium-titanium resources in the vanadium-titanium magnetite, and respectively obtain titanium tetrachloride and ferrovanadium alloy products, and has the advantages of high resource utilization rate, energy conservation, consumption reduction, environmental friendliness, high product added value and the like.)

1. A method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite comprises a cyclone preheating process (1), a fluidized bed prereduction process (2), an electric furnace melting and separating process (3), a vanadium blowing process (4), a cooling and crushing process (5), a granulation and screening process (6), a fluidization chlorination process (7), a refining vanadium-removing process (8), an oxidation treatment process (9) and a vanadium-iron smelting process (10), and the method comprises the following steps:

1) sending the vanadium titano-magnetite into a cyclone preheating process (1), exchanging heat with high-temperature fluidized bed flue gas from a fluidized bed pre-reduction process (2), sending the vanadium titano-magnetite after heat exchange into the fluidized bed pre-reduction process (2), and sending tail gas of the cyclone preheating process to be subjected to environment-friendly treatment;

2) in the fluidized bed pre-reduction process (2), reducing agents come from electric furnace gas in the electric furnace melting process (3) and supplemented reducing gas, and the vanadium titano-magnetite is pre-reduced and then is fed into the electric furnace melting process (3);

3) in the electric furnace melting and separating process (3), the pre-reduced vanadium titano-magnetite reacts under the action of a solid reducing agent to obtain vanadium-containing molten iron and vanadium-containing titanium slag; sending the vanadium-containing molten iron to a vanadium blowing process (4) for vanadium blowing operation to obtain semisteel and vanadium slag, and returning the vanadium slag to an electric furnace melting process (3);

4) the vanadium-titanium-containing slag obtained in the electric furnace melting and separating process (3) is sent to a cooling and crushing process (5), and the vanadium-titanium-containing slag fine powder obtained by crushing is sent to a granulating and screening process (6);

5) in the granulating and screening process (6), adding carbon powder and binder into the vanadium-containing titanium slag fine powder, uniformly mixing, pressing and molding, performing heat treatment and solidification, and crushing and screening to obtain a raw material of a fluidized chlorination process (7);

6) in the fluidized chlorination procedure (7), under the action of a catalyst, reacting the vanadium-containing titanium slag powder with chlorine to obtain vanadium-containing titanium tetrachloride and chlorination tailings, and carrying out environment-friendly treatment on the chlorination tailings;

7) in the refining vanadium-removing procedure (8), the titanium tetrachloride containing vanadium is purified to remove vanadium to obtain a titanium tetrachloride product and vanadium-removing slag;

8) in the oxidation treatment process (9), the vanadium-removing slag is oxidized under the action of air and water to obtain vanadium-removing dry slag;

9) in the ferrovanadium smelting process (10), vanadium-removing dry slag, steel scrap and a reducing agent are added to smelt to obtain ferrovanadium alloy.

2. The method for comprehensively utilizing the vanadium-titanium magnetite-vanadium-titanium resource as claimed in claim 1, wherein the operating temperature of the fluidized bed pre-reduction process (2) is 600 ℃ to 960 ℃, and the reduction gas is one or more of blast furnace gas, coke oven gas, electric furnace gas, coal gas or methane reforming gas.

3. The method for comprehensively utilizing the vanadium-titanium resources of the vanadium-titanium magnetite as claimed in claim 1, wherein the solid reducing agent in the electric furnace melting and separating process (3) is one or more of pulverized coal, metallurgical coke, activated carbon or petroleum coke; in the melting and separating process of the electric furnace, the operation temperature is 1400-1800 ℃, and the addition amount of the solid reducing agent is 10-40% of the mass of the vanadium-titanium magnetite.

4. The method for comprehensively utilizing the vanadium-titanium magnetite vanadium-titanium resource as claimed in claim 1, wherein in the cooling and crushing step (5), the vanadium-titanium containing slag is crushed to obtain the vanadium-titanium containing slag fine powder with the average particle size of less than 80 μm.

5. The method for comprehensively utilizing the vanadium-titanium magnetite-vanadium-titanium resource as claimed in claim 1, wherein in the granulating and screening process (6), the carbon powder refers to one or more of activated carbon, metallurgical coke, petroleum coke and coal powder, and the average particle size of the carbon powder is less than 50 μm; the binder is one or more of phenolic resin, sucrose, starch, asphalt and polyvinyl alcohol.

6. The method for comprehensively utilizing the vanadium-titanium resources of the vanadium-titanium magnetite as claimed in claim 1, wherein in the granulating and screening process (6), the vanadium-titanium-containing slag fine powder is added with carbon powder and a binder, the adding mass of the carbon powder is 10-50% of that of the vanadium-titanium-containing slag fine powder, the adding mass of the binder is 1-10% of that of the vanadium-titanium-containing slag fine powder, and the fluidized chlorinated raw materials are obtained by press forming, high-temperature curing, crushing and screening after uniform mixing; in the granulating and screening process (6), the pressure is 0.3MPa-20MPa, the curing temperature is 100-900 ℃, and the screening average grain diameter is 50-300 mu m.

7. The method for comprehensively utilizing the vanadium-titanium magnetite-vanadium-titanium resource as claimed in claim 1, wherein in the fluidized chlorination step (7), the chlorination temperature is 350 ℃ to 700 ℃ and the average residence time is 30min to 240 min.

8. The method for comprehensively utilizing the vanadium-titanium magnetite-vanadium-titanium resource as claimed in claim 1, wherein in the fluidization chlorination step (7), the catalyst is carbon monoxide or methane, and the addition amount of the catalyst is 0.01-3% of the mass of the vanadium-titanium containing slag fine powder.

9. The method for comprehensively utilizing the vanadium-titanium magnetite-vanadium-titanium resource as claimed in claim 1, wherein the oxidation treatment step (9) is carried out at an operating temperature of 300 to 800 ℃ for an oxidation time of 30 to 180 min.

10. The method for comprehensively utilizing the vanadium-titanium resources of the vanadium-titanium magnetite as claimed in claim 1, wherein in the vanadium-iron smelting process (10), the reducing agent is ferrosilicon and/or aluminum, the addition amount of steel scraps is 5-30% of the mass of the vanadium-removing dry slag, the addition amount of the reducing agent is 15-30% of the mass of the vanadium-removing dry slag, and the smelting temperature is 1500-1700 ℃.

Technical Field

The invention belongs to the fields of chemical industry and metallurgy, and particularly relates to a method for comprehensively utilizing vanadium-titanium magnetite resources.

Background

China is a large vanadium-titanium resource country, and the vanadium-titanium mineral reserves account for more than 35 percent of the world. Vanadium titano-magnetite is the predominant form in which it exists. The vanadium titano-magnetite is an important strategic vanadium-titanium resource in China.

At present, the vanadium titano-magnetite in China mainly adopts a blast furnace smelting process. Adding common iron ore into the vanadium-titanium magnetite, feeding the vanadium-titanium magnetite into a blast furnace for smelting to obtain vanadium-containing molten iron and titanium-containing blast furnace slag, and blowing the vanadium-containing molten iron to obtain vanadium slag and semisteel. Vanadium pentoxide and vanadium extraction tailings are obtained from the vanadium slag through a sodium treatment or calcification path. The existing vanadium-titanium magnetite vanadium resource utilization process mainly has the following problems: (1) in the blast furnace smelting process, about 30 percent of vanadium enters the titanium-containing blast furnace slag, and the vanadium resource is not effectively utilized at present. (2) In the process of extracting vanadium from vanadium slag, a sodium treatment/calcification process flow is generally adopted. The sodium content of the sodium-modified vanadium extraction tailings is high, the sulfur content of the calcified vanadium extraction tailings is high, and the calcified vanadium extraction tailings are difficult to return to the blast furnace smelting process, so that a large amount of solid hazardous waste is caused, and the environment is polluted. (3) The traditional sodium treatment/calcification vanadium extraction process is mainly a wet process, and generates a large amount of ammonia nitrogen wastewater along with the production of the ammonia nitrogen wastewater, thereby bringing about a serious environmental pollution problem. (4) Currently the main application area of vanadium is ferrovanadium. The vanadium slag needs to be subjected to a long wet process to obtain vanadium pentoxide. And vanadium pentoxide is used as a raw material to produce ferrovanadium, so that the production process is long and the pollution is great. In order to solve the problem of low utilization rate of vanadium resources of the existing vanadium titano-magnetite, researchers explore a new process for improving the utilization efficiency. Chinese patent application CN105986126B and chinese patent application CN109835949A disclose methods for producing vanadium pentoxide by a vanadium slag chlorination process, respectively. The chlorination process has short vanadium extraction process flow, the obtained vanadium pentoxide has high purity, and then the vanadium pentoxide can be used as a raw material to produce ferrovanadium, but the problems of long production flow and high treatment difficulty of chlorination tailings still exist.

The current titanium resourceThere are two main ways of utilizing (i.e., fluidized chlorination) and sulfuric acid processes. The fluidized chlorination refers to the carbon-blending chlorination of a titanium-containing material in a fluidized bed reactor to obtain a titanium tetrachloride intermediate product. Titanium tetrachloride can be oxidized to produce titanium dioxide, and also can be reduced by magnesium to produce titanium sponge. The fluidized chlorination process has short flow, low cost and little pollution, and is a mainstream titanium resource utilization technology. But the fluidization chlorination has high requirements on raw materials, the grade of the titanium dioxide is over 90 percent, and the particle size is over 90 percent in the range of 75-300 mu m. The operating temperature of the fluidization chlorination process is generally 800-1000 ℃, and at the temperature, impurities such as CaO, MgO and the like in the raw materials can be chlorinated to generate molten CaCl₂And MgCl₂Binding the material and disrupting normal fluidization. Generally, the content of CaO in the chlorinated raw material is required to be less than 0.3%, and the content of MgO in the chlorinated raw material is required to be less than 1.2%. The sulfuric acid process is to dissolve titanium-containing material in sulfuric acid system to obtain titanyl sulfate and produce titanium white powder through hydrolysis. The sulfuric acid process is usually carried out on titanium concentrates (TiO)₂Grade about 50%) or acid-soluble titanium slag (TiO)₂The grade is about 70 percent) is used as raw materials, the energy consumption in the production process is high, the pollution is large, and the technology is eliminated internationally. In the current blast furnace smelting process, titanium in vanadium titano-magnetite enters blast furnace slag, wherein the titanium contains TiO₂About 22% CaO, about 8% MgO, and Al₂O₃About 15 percent, because the titanium grade is low, the content of impurities such as calcium, magnesium and the like is high, the titanium resource can not be effectively utilized at present.

In order to solve the problem of low utilization rate of the titanium resource of the existing vanadium titano-magnetite, researchers explore a new process for improving the utilization efficiency. Chinese patent CN101418383B discloses a method for preparing TiCl from titanium-containing slag₄The method of (1). In the patent, titanium dioxide in blast furnace slag is converted into titanium carbide by adding a reducing agent within the range of 1200-1500 ℃, and then low-temperature chlorination is carried out within the range of 300-650 ℃ in a low-temperature area. The low-temperature chlorination of titanium carbide can greatly reduce the chlorination of calcium and magnesium, and the reaction temperature is lower than the melting temperature of calcium and magnesium chloride, so that the problem of bonding and fluid loss is solved. But the high-temperature carbonization energy consumption is very high, and the problem of incomplete carbonization often exists. Titanium carbide is chloridized at low temperature, the heat release is large, furnace temperature fluctuation in the production operation process is caused, and the control complexity is increased. And low-grade blast furnace slag is directly chlorinated to generate a large amount of chlorinated tailings, so that a better solution is not provided for the moment. The Chinese patent application CN108677025A discloses a method for extracting titanium from titanium-containing blast furnace slag. In the patent, titanium dioxide in blast furnace slag is subjected to nitridation reaction at the temperature of 800-1200 ℃ in an ammonia atmosphere to obtain nitrided slag containing titanium nitride. Then reacting with chlorine at the low temperature of 250-600 ℃ to generate titanium tetrachloride. The process also has the problems of high nitriding energy consumption, incomplete reaction and large amount of chlorinated tailings. And the nitrogen slag is easy to form explosive nitrogen trichloride compounds in a chlorine-containing system, thereby bringing potential safety hazards.

Aims to solve the problems of low titanium-containing grade in the blast furnace slag and difficult efficient utilization. Researchers have explored new processes for direct reduction. The Chinese patent application 201910299575.0 discloses a method for comprehensive utilization of vanadium titano-magnetite by deep reduction short-process smelting, which adopts a rotary kiln for pre-reduction and a smelting furnace for reduction and melting to obtain iron-containing water and titanium slag. The Chinese patent application 201910319150.1 discloses a method for simultaneously preparing titanium slag and vanadium-containing pig iron by using vanadium-titanium magnetite as a raw material, wherein the vanadium-titanium magnetite is directly smelted by an electric furnace to obtain molten iron and titanium slag. The Chinese patent application 201810531355.1 discloses a method for smelting vanadium-titanium magnetite by using a HIsmelt smelting reduction process, wherein preheated and pre-reduced vanadium-titanium magnetite is directly injected into a furnace through an ore gun of a HIsmelt smelting reduction furnace to obtain vanadium-containing molten iron and titanium slag. Titanium slag with titanium dioxide grade of about 50 percent can be obtained by a direct reduction technology. However, the 50 titanium slag still cannot be used as a raw material of the existing high-temperature fluidized chlorination or sulfuric acid process. Therefore, researchers propose that the grade of the titanium slag is further improved by adopting a beneficiation method. The Chinese patent application CN102061393A discloses a titanium slag deep processing method. The patent utilizes the titanium slag of a high-temperature electric furnace, further raises the heat temperature to 1600-1750 ℃, and carries out heat preservation, so that the black titanium ore mineral grains in the titanium slag grow up, and the black titanium ore mineral grains begin to be cooled after the average grain diameter is larger than 80 mu m. Crushing and floating the cooled titanium slagObtaining upgraded titanium slag with the grade of about 75%. The Chinese invention patent CN107653380B discloses a method for regulating and controlling the crystallization phase of molten titanium slag. Regulating and controlling titanium slag components, slowly cooling to 1300-1500 ℃ for quenching treatment, and reselecting to obtain TiO₂The grade of upgraded titanium slag is 76%. The upgrading of the titanium slag has the problems of high energy consumption and low recovery rate. And the upgraded titanium slag can only be used as a raw material of the sulfate process titanium dioxide. If the 'high-temperature carbonization/nitridation-low-temperature chlorination' process is adopted to treat the 50 or 70 titanium slag, although the reaction temperature can be reduced, a large amount of heat is released by high-grade carbon/titanium nitride in the low-temperature chlorination process, and the heat transfer problem of the reactor is difficult to solve.

In conclusion, the existing vanadium-titanium magnetite vanadium resource utilization has the problems of long process, heavy pollution and large tailing amount. The utilization of titanium resources has the problems of high energy consumption, long process flow and low yield. And the vanadium-titanium extraction is respectively carried out in two different process systems, the process is long, and the operation is complex.

Disclosure of Invention

Aiming at the problems, the invention provides a method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite. By adopting the method, the vanadium-titanium synchronous extraction is realized by changing the extraction path of vanadium, and the vanadium and the titanium are respectively utilized, so that the utilization efficiency of the vanadium and the titanium is obviously improved, the process flow is greatly shortened, the added value of products is improved, the environmental pollution is reduced, and the method has obvious economic benefit and social benefit.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite comprises a cyclone preheating process 1, a fluidized bed prereduction process 2, an electric furnace melting process 3, a vanadium blowing process 4, a cooling and crushing process 5, a granulation screening process 6, a fluidization chlorination process 7, a refining vanadium-removing process 8, an oxidation treatment process 9 and a vanadium-iron smelting process 10, and the method comprises the following steps:

1) sending the vanadium titano-magnetite into a cyclone preheating process 1, exchanging heat with the high-temperature fluidized bed flue gas from a fluidized bed pre-reduction process 2, sending the vanadium titano-magnetite after heat exchange into the fluidized bed pre-reduction process 2, and sending tail gas of the cyclone preheating process to environment-friendly treatment;

2) in the fluidized bed pre-reduction process 2, the reducing agent is from the electric furnace gas in the electric furnace melting and separating process 3 and supplemented reducing gas, and the vanadium titano-magnetite is pre-reduced and then is fed into the electric furnace melting and separating process 3;

3) in the electric furnace melting and separating process 3, the pre-reduced vanadium titano-magnetite reacts under the action of a solid reducing agent to obtain vanadium-containing molten iron and vanadium-containing titanium slag; sending the vanadium-containing molten iron to a vanadium blowing process 4 for vanadium blowing operation to obtain semisteel and vanadium slag, and returning the vanadium slag to an electric furnace melting process 3;

4) the vanadium-titanium-containing slag obtained in the electric furnace melting and separating process 3 is sent to a cooling and crushing process 5, and the fine powder obtained by crushing is sent to a granulating and screening process 6;

5) in the granulation screening process 6, the vanadium-titanium-containing slag fine powder is mixed with carbon powder and a binder, and the mixture is uniformly mixed, pressed, molded, thermally treated, solidified, crushed and screened to obtain a raw material-vanadium-titanium-containing slag powder material of the fluidization chlorination process 7;

6) in the fluidized chlorination procedure 7, under the action of a catalyst, reacting the vanadium-containing titanium slag powder with chlorine to obtain vanadium-containing titanium tetrachloride and chlorination tailings, and carrying out environment-friendly treatment on the chlorination tailings;

7) in the refining vanadium-removing process 8, the titanium tetrachloride containing vanadium is purified to remove vanadium to obtain a titanium tetrachloride product and vanadium-removing slag;

8) in the oxidation treatment process 9, the vanadium-removing slag is oxidized under the action of air and water to obtain vanadium-removing dry slag;

9) in the ferrovanadium smelting process 10, the vanadium-removed dry slag is added with steel scrap and a reducing agent to be smelted to obtain ferrovanadium alloy.

Preferably, the operating temperature of the fluidized bed pre-reduction process 2 is 600-960 ℃, and the reduction gas is one or more of blast furnace gas, coke oven gas, electric furnace gas, coal gas or methane reforming gas.

Preferably, the solid reducing agent in the electric furnace melting and separating process 3 is one or more of coal powder, metallurgical coke, activated carbon or petroleum coke; in the melting and separating process of the electric furnace, the operation temperature is 1400-1800 ℃, and the addition amount of the solid reducing agent is 10-40% of the mass of the vanadium-titanium magnetite.

Preferably, the vanadium slag obtained in the vanadium blowing step 4 is returned to the electric furnace melting step 3 again.

Preferably, in the cooling and crushing step 5, the vanadium-titanium containing slag is crushed to obtain vanadium-titanium containing slag fine powder with an average particle size of less than 80 μm, more preferably, an average particle size of less than 50 μm, and even more preferably, an average particle size of less than 30 μm.

Preferably, in the granulating and screening process 6, the carbon powder refers to one or more of activated carbon, metallurgical coke, petroleum coke and coal powder, and the average particle size of the carbon powder is less than 50 μm, more preferably less than 35 μm, and still more preferably less than 25 μm; the binder is one or more of phenolic resin, sucrose, starch, asphalt and polyvinyl alcohol.

Preferably, in the granulating and screening step 6, the vanadium-titanium-containing slag fine powder is added with carbon powder and a binder, wherein the adding mass of the carbon powder is 10-50% of the mass of the vanadium-titanium-containing slag fine powder, the adding mass of the binder is 1-10% of the mass of the vanadium-titanium-containing slag fine powder, and the fluidized chlorination raw material is obtained by uniformly mixing, pressing, curing at high temperature, crushing and screening; in the granulating and screening process 6, the pressure is 0.3MPa-20MPa, the curing temperature is 100-900 ℃, and the screening average grain diameter is 50-300 μm.

Preferably, in the fluidized chlorination process 7, the chlorination temperature is 350 ℃ to 700 ℃, the average residence time is 30min to 240min, and further preferably, the chlorination temperature is 400 ℃ to 600 ℃.

Preferably, in the fluidized chlorination process 7, the catalyst is carbon monoxide or methane, and the addition amount of the catalyst is 0.01-3% of the mass of the vanadium-titanium-containing slag fine powder.

Preferably, in the oxidation treatment step 9, the operation temperature is 300 to 800 ℃, and the oxidation time is 30 to 180 min.

Preferably, in the ferrovanadium smelting process 10, the reducing agent refers to ferrosilicon and/or aluminum, the addition amount of the steel scrap is 5-30% of the mass of the vanadium-removing dry slag, the addition amount of the reducing agent is 15-30% of the mass of the vanadium-removing dry slag, and the smelting temperature is 1500-1700 ℃.

Compared with the prior art, the invention has the following outstanding advantages:

(1) the flue gas of the fluidized bed prereduced high-temperature fluidized bed is used for preheating materials, so that the high-efficiency utilization of heat is realized.

(2) The electric furnace gas generated by electric furnace melting is used as a reducing agent for fluidized bed prereduction, and the sensible heat and latent heat of the flue gas are utilized to improve the energy utilization efficiency.

(3) The vanadium slag generated in the vanadium blowing process returns to the electric furnace melting process, so that the vanadium extraction path is changed, and the problem that the vanadium extraction tailings are difficult to utilize is solved.

(4) The vanadium-containing titanium slag is granulated by mixing carbon powder, so that the ore/carbon contact effect is improved, the chlorination reaction temperature is reduced by coupling catalytic chlorination, the problem of calcium and magnesium loss is solved, and the material adaptability of the process is improved.

(5) The extraction path of vanadium in the vanadium-titanium magnetite is changed, vanadium is extracted from the vanadium-containing titanium slag, and the utilization efficiency of the vanadium is obviously improved.

(6) The low-temperature chlorination of the low-grade titanium-rich material is realized, the utilization of high-calcium magnesium titanium resources is realized, and the utilization efficiency of titanium is obviously improved.

(7) The vanadium-removing dry slag is used as a raw material to directly produce the ferrovanadium, so that the process flow is obviously shortened, the utilization value of vanadium is improved, and the production cost of the ferrovanadium is reduced.

The invention develops a new process flow through technological innovation. The vanadium slag obtained in the vanadium blowing process is returned to the electric furnace melting process, so that the vanadium is separated from the titanium slag, the extraction path of the vanadium is changed, the vanadium and titanium are extracted together, and the problem of treatment of vanadium extraction tailings is thoroughly solved. The crushing particle size of the vanadium-containing titanium slag is controlled, fine carbon powder and a binder are added for granulation, ore/carbon contact is strengthened, catalytic chlorination is coupled, chlorination reaction temperature is reduced, and the problem of utilization of high-calcium magnesium titanium resources is solved. The vanadium ferrovanadium alloy is directly smelted by adding the reducing agent and the steel scrap into the titanium tetrachloride vanadium-removing dry slag, so that the preparation of a vanadium pentoxide intermediate product is omitted, the flow is greatly shortened, and the production cost is reduced. The method for comprehensively utilizing the vanadium-titanium resources of the vanadium-titanium magnetite provided by the invention has important significance for realizing the high-efficiency utilization of the vanadium-titanium resources in the vanadium-titanium magnetite.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.

FIG. 1 is a schematic flow chart of a method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite according to the present invention.

Reference numerals: 1. the method comprises the following steps of cyclone treatment, 2, fluidized bed pre-reduction, 3, electric furnace melting and separating, 4, vanadium blowing, 5, cooling and crushing, 6, granulation and screening, 7, fluidization chlorination, 8, refining and vanadium removal, 9, oxidation treatment, 10 and ferrovanadium smelting.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. It should be noted that the examples are only for illustrating the technical solutions of the present invention, and not for limiting the same.

FIG. 1 is a schematic flow chart of a method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite according to the present invention.

Example 1

With reference to fig. 1, the method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite used in this embodiment includes a cyclone preheating step 1, a fluidized bed prereduction step 2, an electric furnace melting step 3, a vanadium blowing step 4, a cooling and crushing step 5, a granulation and screening step 6, a fluidization chlorination step 7, a refining and vanadium-removing step 8, an oxidation treatment step 9, and a vanadium-iron smelting step 10, and the method is performed according to the following steps:

1) sending the vanadium titano-magnetite into a cyclone preheating process 1, exchanging heat with the high-temperature fluidized bed flue gas from a fluidized bed pre-reduction process 2, sending the vanadium titano-magnetite after heat exchange into the fluidized bed pre-reduction process 2, and sending tail gas of the cyclone preheating process to environment-friendly treatment;

2) in the fluidized bed pre-reduction process 2, the reducing agent is from the electric furnace gas in the electric furnace melting and separating process 3 and supplemented reducing gas, and the vanadium titano-magnetite is pre-reduced and then is fed into the electric furnace melting and separating process 3;

3) in the electric furnace melting and separating process 3, the pre-reduced vanadium titano-magnetite reacts under the action of a solid reducing agent to obtain vanadium-containing molten iron and vanadium-containing titanium slag; sending the vanadium-containing molten iron to a vanadium blowing process 4 for vanadium blowing operation to obtain semisteel and vanadium slag, and returning the vanadium slag to an electric furnace melting process 3;

4) the vanadium-titanium-containing slag obtained in the electric furnace melting and separating process 3 is sent to a cooling and crushing process 5, and the fine powder obtained by crushing is sent to a granulating and screening process 6;

5) in the granulating and screening process 6, the vanadium-containing titanium slag fine powder is mixed with carbon powder and a binder, the mixture is uniformly mixed and then is pressed and molded, the mixture is subjected to heat treatment and solidification, and the raw material of the fluidized chlorination process 7 is obtained after crushing and screening, wherein the raw material is the vanadium-containing titanium slag powder;

6) in the fluidized chlorination procedure 7, under the action of a catalyst, reacting the vanadium-containing titanium slag powder with chlorine to obtain vanadium-containing titanium tetrachloride and chlorination tailings, and carrying out environment-friendly treatment on the chlorination tailings;

7) in the refining vanadium-removing process 8, the titanium tetrachloride containing vanadium is purified to remove vanadium to obtain a titanium tetrachloride product and vanadium-removing slag;

8) in the oxidation treatment process 9, the vanadium-removing slag is oxidized under the action of air and water to obtain vanadium-removing dry slag;

9) in the ferrovanadium smelting process 10, the vanadium-removed dry slag is added with steel scrap and a reducing agent to be smelted to obtain ferrovanadium alloy.

Example 2

In this embodiment, the method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite described in embodiment 1 is adopted, and in the fluidized bed pre-reduction process 2, the operation temperature is 600 ℃, the reduction gas is blast furnace gas, and the metallization rate is 10%. The solid reducing agent in the electric furnace melting and separating process 3 is coal powder, the operating temperature is 1400 ℃, the adding amount of the solid reducing agent is 10 percent of the mass of the vanadium-titanium magnetite, and the concentration of vanadium in the titanium slag is 1 time of that in the molten iron. And the vanadium slag obtained in the vanadium blowing step 4 returns to the electric furnace melting step 3 again. In the cooling and crushing step 5, the average particle size of the crushed vanadium-containing titanium slag is 0.1 μm. In the granulating and screening step 6, activated carbon with an average particle size of 0.1 μm is used as carbon powder, and phenolic resin is used as a binder. In the granulating and screening process 6, the adding mass of carbon powder is 10% of the mass of the vanadium-titanium-containing slag fine powder, the adding mass of the binder is 1% of the mass of the vanadium-titanium-containing slag fine powder, the fluidized chlorinated raw materials are obtained by pressing, high-temperature curing, crushing and screening after uniform mixing, wherein the pressure is 0.3MPa, the curing temperature is 100 ℃, and the screening average particle size is 50 μm. In the fluidized chlorination procedure 7, the chlorination temperature is 350 ℃, the average retention time is 240min, the catalyst is carbon monoxide, the addition amount of the catalyst is 0.01 percent of the mass of the vanadium-titanium-containing slag fine powder, and the chlorination rate of titanium dioxide is 90 percent. In the oxidation treatment process 9, the operation temperature is 300 ℃, and the oxidation time is 180 min. In the ferrovanadium smelting process 10, the reducing agents refer to 75 ferrosilicon and aluminum, the addition amount of steel scrap is 5% of the mass of the vanadium-removing dry slag, the addition amount of 75 ferrosilicon is 15% of the mass of the vanadium-removing dry slag, the addition amount of aluminum is 15% of the mass of the vanadium-removing dry slag, the smelting temperature is 1500 ℃, and the vanadium-containing mass fraction of the obtained ferrovanadium alloy is 80%.

Example 3

In this embodiment, the method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite ore described in embodiment 1 is adopted, and in the fluidized bed pre-reduction process 2, the operation temperature is 960 ℃, the reduction gas is reformed methane gas, and the metallization rate is 60%. The solid reducing agent in the electric furnace melting and separating process 3 is petroleum coke, the operating temperature is 1800 ℃, the adding amount of the solid reducing agent is 40 percent of the mass of the vanadium-titanium magnetite, and the concentration of vanadium in the titanium slag is 5 times of that in the molten iron. And the vanadium slag obtained in the vanadium blowing step 4 returns to the electric furnace melting step 3 again. In the cooling and crushing step 5, the average particle size of the crushed vanadium-containing titanium slag is 50 μm. In the granulating and screening process 6, coal powder with the average particle size of 50 microns is used as carbon powder, and polyvinyl alcohol is used as a binder. In the granulating and screening process 6, the adding mass of carbon powder is 50% of the mass of the vanadium-titanium-containing slag fine powder, the adding mass of the binder is 10% of the mass of the vanadium-titanium-containing slag fine powder, the fluidized chlorinated raw materials are obtained by pressing, curing at high temperature, crushing and screening after being uniformly mixed, wherein the pressure is 20MPa, the curing temperature is 900 ℃, and the screening average particle size is 300 mu m. In the fluidized chlorination procedure 7, the chlorination temperature is 700 ℃, the average retention time is 30min, the catalyst is carbon monoxide, the addition amount of the catalyst is 3% of the mass of the vanadium-titanium-containing slag fine powder, and the chlorination rate of titanium dioxide is 98%. In the oxidation treatment process 9, the operation temperature is 800 ℃, and the oxidation time is 30 min. In the ferrovanadium smelting process 10, the reducing agent is metal aluminum, the addition amount of steel scrap is 30% of the mass of the vanadium-removing dry slag, the addition amount of aluminum is 30% of the mass of the vanadium-removing dry slag, the smelting temperature is 1700 ℃, and the vanadium-containing mass fraction of the obtained ferrovanadium alloy is 40%.

Example 4

In this embodiment, the method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite described in embodiment 1 is adopted, and in the fluidized bed prereduction process 2, the operation temperature is 660 ℃, the reduction gas is coke oven gas, and the metallization rate is 30%. The solid reducing agent in the electric furnace melting and separating process 3 is a mixture of metallurgical coke and active carbon, the operation temperature is 1600 ℃, the addition amount of the solid reducing agent is 20 percent of the mass of the vanadium-titanium magnetite, and the concentration of vanadium in the titanium slag is 4 times of that of vanadium in the molten iron. And the vanadium slag obtained in the vanadium blowing step 4 returns to the electric furnace melting step 3 again. In the cooling and crushing step 5, the average particle size of the crushed vanadium-containing titanium slag is 20 μm. In the granulating and screening step 6, metallurgical coke with an average particle size of 20 μm is used as carbon powder, and sucrose is used as a binder. In the granulating and screening process 6, the adding mass of carbon powder is 20% of the mass of the vanadium-titanium-containing slag fine powder, the adding mass of the binder is 3% of the mass of the vanadium-titanium-containing slag fine powder, the fluidized chlorinated raw materials are obtained by pressing, high-temperature curing, crushing and screening after uniform mixing, wherein the pressure is 7MPa, the curing temperature is 400 ℃, and the screening average particle size is 100 mu m. In the fluidized chlorination procedure 7, the chlorination temperature is 500 ℃, the average retention time is 60min, the catalyst is methane, the addition amount of the catalyst is 0.01 percent of the mass of the vanadium-titanium-containing slag fine powder, and the chlorination rate of titanium dioxide is 95 percent. In the oxidation treatment step 9, the operation temperature is 500 ℃ and the average residence time is 60 min. In the ferrovanadium smelting process 10, the reducing agents refer to 75 ferrosilicon and aluminum, the addition amount of steel scrap is 10% of the mass of the vanadium-removing dry slag, the addition amount of 75 ferrosilicon is 20% of the mass of the vanadium-removing dry slag, the addition amount of aluminum is 20% of the mass of the vanadium-removing dry slag, the smelting temperature is 1600 ℃, and the obtained ferrovanadium alloy contains vanadium with the mass fraction of 60%.

Example 5

In this embodiment, the method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite described in embodiment 1 is adopted, and in the fluidized bed prereduction process 2, the operation temperature is 660 ℃, the reduction gas is electric furnace gas, and the metallization rate is 25%. The solid reducing agent in the electric furnace melting and separating process 3 is an activated carbon mixture, the operating temperature is 1500 ℃, the adding amount of the solid reducing agent is 25 percent of the mass of the vanadium-titanium magnetite, and the concentration of vanadium in the titanium slag is 3 times of that in the molten iron. And the vanadium slag obtained in the vanadium blowing step 4 returns to the electric furnace melting step 3 again. In the cooling and crushing step 5, the average particle size of the crushed vanadium-containing titanium slag is 20 μm. In the granulating and screening process 6, petroleum coke with the average particle size of 20 microns is used as carbon powder, and asphalt is used as a binder. In the granulating and screening process 6, the adding mass of carbon powder is 20% of the mass of the vanadium-titanium-containing slag fine powder, the adding mass of the binder is 3% of the mass of the vanadium-titanium-containing slag fine powder, the fluidized chlorinated raw materials are obtained by pressing, high-temperature curing, crushing and screening after uniform mixing, wherein the pressure is 7MPa, the curing temperature is 400 ℃, and the screening average particle size is 100 mu m. In the fluidized chlorination procedure 7, the chlorination temperature is 500 ℃, the average retention time is 70min, the catalyst is methane, the addition amount of the catalyst is 3% of the mass of the vanadium-containing titanium slag fine powder, and the chlorination rate of titanium dioxide is 93%. In the oxidation treatment step 9, the operation temperature is 500 ℃ and the average residence time is 70 min. In the ferrovanadium smelting process 10, the reducing agents refer to 75 ferrosilicon and aluminum, the addition amount of steel scrap is 11% of the mass of the vanadium-removing dry slag, the addition amount of 75 ferrosilicon is 21% of the mass of the vanadium-removing dry slag, the addition amount of aluminum is 21% of the mass of the vanadium-removing dry slag, the smelting temperature is 1650 ℃, and the vanadium-containing mass fraction of the obtained ferrovanadium alloy is 55%.

Example 6

In this embodiment, the method for comprehensively utilizing vanadium-titanium resources of vanadium-titanium magnetite ore described in embodiment 1 is adopted, and in the fluidized bed pre-reduction process 2, the operation temperature is 660 ℃, the reduction gas is coal gas, and the metallization rate is 20%. The solid reducing agent in the electric furnace melting and separating process 3 is an activated carbon mixture, the operation temperature is 1450 ℃, the addition amount of the solid reducing agent is 28 percent of the mass of the vanadium-titanium magnetite, and the concentration of vanadium in titanium slag is 2 times of that in molten iron. And the vanadium slag obtained in the vanadium blowing step 4 returns to the electric furnace melting step 3 again. In the cooling and crushing step 5, the average particle size of the crushed vanadium-containing titanium slag is 20 μm. In the granulating and screening process 6, petroleum coke with the average particle size of 20 microns is used as carbon powder, and starch is used as a binder. In the granulating and screening process 6, the adding mass of carbon powder is 20% of the mass of the vanadium-titanium-containing slag fine powder, the adding mass of the binder is 3% of the mass of the vanadium-titanium-containing slag fine powder, the fluidized chlorinated raw materials are obtained by pressing, high-temperature curing, crushing and screening after uniform mixing, wherein the pressure is 7MPa, the curing temperature is 400 ℃, and the screening average particle size is 100 mu m. In the fluidized chlorination procedure 7, the chlorination temperature is 500 ℃, the average retention time is 60min, the catalyst is carbon monoxide, the addition amount of the catalyst is 0.1 percent of the mass of the vanadium-titanium-containing slag fine powder, and the chlorination rate of titanium dioxide is 96 percent. In the oxidation treatment step 9, the operation temperature is 500 ℃ and the average residence time is 60 min. In the ferrovanadium smelting process 10, the reducing agents refer to 75 ferrosilicon and aluminum, the addition amount of steel scrap is 11% of the mass of the vanadium-removing dry slag, the addition amount of 75 ferrosilicon is 21% of the mass of the vanadium-removing dry slag, the addition amount of aluminum is 21% of the mass of the vanadium-removing dry slag, the smelting temperature is 1650 ℃, and the vanadium-containing mass fraction of the obtained ferrovanadium alloy is 55%.

The invention has not been described in detail and is within the skill of the art.

The present invention may be embodied in many different forms and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.