阅读说明：本技术 一种从高钛型高炉渣水淬渣中富集提取钛的方法 (Method for enriching and extracting titanium from high-titanium blast furnace slag water-quenched slag ) 是由 李崇瑛 涂冬林 王意茹 于 2021-01-20 设计创作，主要内容包括：本发明涉及一种从高钛型高炉渣水淬渣中富集提取钛的方法,具体工艺包括以下步骤：(1)前处理：将水淬渣干燥、破碎、研磨,筛分后得到所需粒径的原料；(2)混合：将水淬渣与熔剂、助熔剂按照一定比例混合均匀；(3)熔融：在设定的化学反应温度区间内进行反应；(4)溶解：将所得块状熔融固体与水按固液质量比混合,在恒定的温度区间内充分搅拌浸取；(5)过滤：采用真空减压抽滤,进行分离,得到富钛液与滤渣。本发明的关键在于首次采用硫酸钠与硫酸氢钠作为助熔剂,用于水淬渣中钛的提取与富集工艺,达到了较好的效果。与传统硫酸法相比,工艺流程简短,且生产成本低,环保,大大减少了对环境的污染与损害。(The invention relates to a method for enriching and extracting titanium from high-titanium blast furnace slag water-quenched slag, which comprises the following steps: (1) pretreatment: drying, crushing, grinding and screening the water-quenched slag to obtain a raw material with a required particle size; (2) mixing: uniformly mixing the water-quenched slag, a flux and a fluxing agent according to a certain proportion; (3) melting: carrying out reaction in a set chemical reaction temperature interval; (4) dissolving: mixing the obtained blocky molten solid with water according to the solid-liquid mass ratio, and fully stirring and leaching in a constant temperature interval; (5) and (3) filtering: and (4) carrying out vacuum reduced pressure suction filtration and separation to obtain a titanium-rich liquid and filter residues. The key point of the invention is that sodium sulfate and sodium bisulfate are used as fluxing agents for the first time and are used for the extraction and enrichment process of titanium in water-quenched slag, thereby achieving better effect. Compared with the traditional sulfuric acid method, the method has the advantages of short process flow, low production cost and environmental protection, and greatly reduces the pollution and damage to the environment.)

1. A method for enriching and extracting titanium by using high titanium type blast furnace slag water quenching slag is characterized by comprising the following process steps and flows:

(1) drying the high titanium blast furnace slag water-quenched slag in an oven, crushing and grinding the high titanium blast furnace slag water-quenched slag by using a planetary ball mill, grinding the high titanium blast furnace slag water-quenched slag to different particle sizes, and screening to obtain the raw material of the required water-quenched slag.

(2) And (3) taking the water-quenched slag obtained in the step (1), and fully and uniformly mixing the water-quenched slag with a flux and a fluxing agent.

(3) And (3) carrying out roasting reaction on the mixed sample obtained in the step (2) at a constant temperature, and then naturally cooling the mixed sample.

(4) And (4) fully mixing the sample obtained in the step (3) with water according to a solid-liquid mass ratio, and fully leaching at a constant temperature.

(5) And (4) filtering and separating the mixed leaching solution obtained in the step (4) under vacuum reduced pressure to obtain a titanium-rich solution and filter residues.

2. The process according to claim 1, wherein the sieve in step (1) has a mesh size of 60 to 320 mesh, and wherein the particle size is 300 to 50 μm, the larger the mesh size, the smaller the particle size.

3. The method as set forth in claim 1, wherein the flux in the step (2) is ammonium sulfate.

4. The method according to claim 1, wherein the flux in the step (2) is sodium sulfate or sodium bisulfate.

5. The method as claimed in claim 1, wherein the mass ratio of the water-quenched slag, the flux and the flux in the step (2) is 2:4 to 16:0 to 7.

6. The method according to claim 1, wherein the calcination temperature of the mixed sample in the step (3) is 380 to 500 ℃.

7. The method as set forth in claim 1, wherein the calcination time in the step (3) is 20min to 120 min.

8. The method of claim 1, wherein the water-leaching assisted separation in step (4) is mechanical agitation.

9. The method according to claim 1, wherein the solid-liquid mass ratio in the step (4) is 1:2 to 6.

10. The method of claim 1, wherein the temperature range of the water leaching in the step (4) is 40 ℃ to 90 ℃.

11. The method according to claim 1, wherein the stirring time of the water-immersed solution in the step (4) is 10 to 60 min.

12. The process of claim 1 wherein the separation in step (4) is by hot filtration.

Technical Field

The invention belongs to the field of resource recycling, and particularly relates to a method for extracting titanium from Panzhihua high-titanium blast furnace slag water-quenched slag.

Background

Titanium has the advantages of higher corrosion resistance, high strength, low density and the like, and is known as space metal. Titanium and its alloy have wide application in the fields of spaceflight, military, medical treatment and the like, so the comprehensive utilization of titanium resources has important significance. China is rich in titanium resources, mainly in the form of vanadium titano-magnetite distributed in Panxi and Chengdu areas, but the utilization rate of titanium is very low. At present, the Panzhihua blast furnace smelting process can only smelt iron and vanadium in vanadium-titanium magnetite, and titanium in the Panzhihua blast furnace smelting process enters blast furnace slag to form special high-titanium blast furnace slag with the titanium content of 22-25%. The titanium-containing blast furnace slag of the Panzhihua in China is gradually increased year by year at the speed of 300-400 million tons per year, and is piled up to hundreds of millions of tons. The titanium-containing blast furnace slag is accumulated in a large amount, so that land resources are occupied, the slag accumulated in the open air is washed by rainwater for a long time, harmful elements in the slag are leached and flow into the underground, underground water pollution is caused, and secondary natural disasters such as debris flow, mountain landslide and the like are easily caused by the accumulation of the slag in a large amount. Therefore, the method can extract and utilize the titanium in the titanium-containing blast furnace slag by an economic and effective method, which has very important significance for resource utilization and environmental protection.

The titanium resource in the titanium-containing blast furnace slag of the Panzhihua vanadium titano-magnetite mainly exists in the forms of titanium dioxide and a small amount of perovskite, most of titanium-containing phases in the blast furnace slag have the characteristics of dispersion, fineness and the like, and are difficult to sort, and the perovskite in the blast furnace slag is relatively stable, low in activity and difficult to process. At present, the comprehensive utilization of the titaniferous blast furnace slag mainly has the following aspects: the titanium dioxide is used as building materials such as cement, mineral wool and the like, and the efficient utilization of the effective component titanium dioxide in the blast furnace slag cannot be realized; secondly, acid leaching is utilized, but the acid leaching has the defects of incomplete leaching, incapability of realizing complete separation of impurities and the like; thirdly, titanium dioxide is extracted by alkali treatment, and the method has large alkali consumption, high energy consumption and difficult realization of industrial production; fourthly, the method for preparing titanium tetrachloride by high-temperature carbonization-low-temperature chlorination has high energy consumption in the high-temperature carbonization process and serious pollution in the low-temperature chlorination process.

In conclusion, the existing methods for extracting and utilizing titanium from titanium-containing blast furnace slag have the defects of complicated process flow, high energy consumption, serious environmental pollution, low resource utilization rate and the like, and a simple, efficient and environment-friendly process method is lacked, so that the development of a simple, low-energy-consumption, environment-friendly and efficient method for extracting and enriching titanium has important significance.

The method utilizes ammonium sulfate as a flux, sodium sulfate and sodium bisulfate as a fluxing agent to extract titanium dioxide in the Panzhihua high titanium type blast furnace slag water-quenched slag, and can convert titanium in the water-quenched slag into a substance which is easy to dissolve in water under the combined action of the flux and the fluxing agent, thereby realizing the high-efficiency extraction and enrichment of titanium in the blast furnace slag, and the method has little influence on the environment.

Disclosure of Invention

The invention aims to solve the technical problem of extracting titanium from the high-titanium blast furnace slag water-quenched slag, and provides a new fluxing agent by taking ammonium sulfate as a fusing agent to react with substances such as magnesium, aluminum, titanium, iron and the like in the high-titanium blast furnace slag water-quenched slag and convert the substances into soluble salts, so that titanium is easier to leach from the slag to obtain enrichment. The process flow is short, strong acid and strong alkali are not introduced, and the method is a clean and efficient invention method.

1. The invention aims to solve the technical problems and aims to extract titanium from high-titanium blast furnace slag water-quenched slag, and is characterized by comprising the following process steps and flows:

(1) drying the high titanium blast furnace slag water-quenched slag in an oven, crushing and grinding the high titanium blast furnace slag water-quenched slag by using a planetary ball mill to different particle sizes, and screening to obtain the required water-quenched slag raw material.

(2) And (3) taking the water-quenched slag obtained in the step (1), and fully and uniformly mixing the water-quenched slag with a flux and a fluxing agent.

(3) And (3) carrying out roasting reaction on the mixed sample obtained in the step (2) at a constant temperature, and then naturally cooling the mixed sample.

(4) And (4) fully mixing the sample obtained in the step (3) with water according to a solid-liquid mass ratio, and fully leaching at a constant temperature.

(5) And (4) filtering and separating the mixed leaching solution obtained in the step (4) under vacuum reduced pressure to obtain a titanium-rich solution and filter residues.

2. The process according to claim 1, wherein the sieve in step (1) has a mesh size of 60 to 320 mesh, and wherein the particle size is 300 to 50 μm, the larger the mesh size, the smaller the particle size.

3. In the above process scheme, the flux in step (2) is ammonium sulfate.

4. In the above process scheme, the fluxing agent in the step (2) is sodium sulfate or sodium bisulfate.

5. In the technical scheme, the mass ratio of the water quenching slag, the flux and the fluxing agent in the step (2) is 2: 4-16: 0-7.

6. In the technical scheme, the roasting temperature range of the mixed sample in the step (3) is 380-500 ℃.

7. In the technical scheme, the roasting time in the step (3) is 20-120 min.

8. In the technical scheme, the water immersion auxiliary separation mode in the step (4) is mechanical stirring, ultrasonic treatment, constant-temperature oscillation and constant-temperature standing.

9. In the technical scheme, the mass ratio of the water immersion liquid in the step (4) is 1: 2-6.

10. In the technical scheme, the temperature range of water leaching in the step (4) is 40-90 ℃.

11. In the technical scheme, the water soaking and stirring time in the step (4) is 10-60 min.

12. In the above process scheme, the separation in step (4) requires filtration while hot.

The method comprises the steps of (1) drying, crushing and grinding; (2) uniformly mixing; (3) roasting; (4) water leaching; (5) and filtering and separating to obtain titanium-rich liquid and filter residue. The key point of the invention is that sodium sulfate and sodium bisulfate are used as fluxing agent for the first time, and under the combined action of the fluxing agent and the fluxing agent, titanium can be leached from slag more easily and is converted into a substance which is easy to dissolve in water.

Compared with the prior art and the method, the method has the following positive effects: in a common system of the action of the flux and the fluxing agent, the titanium element in the water-quenched slag is converted into a substance which is easy to dissolve in water. The sodium sulfate and the sodium bisulfate are firstly used for extracting titanium from the water-quenched slag of the high-titanium blast furnace slag, and the two fluxing agents can improve the system environment of a roasting flux and enable the titanium to be leached in water more easily, thereby achieving the aim of enriching the titanium. The process has the advantages of simple flow, strong operability, environmental protection and great economic and environmental benefits.

Drawings

FIG. 1 is a process flow chart of extracting enriched titanium from Panzhihua high titanium blast furnace slag water-quenched slag.

FIG. 2 is a Scanning Electron Micrograph (SEM) of Panzhihua high titanium blast furnace slag in water quenching.

FIG. 3 is a Scanning Electron Microscope (SEM) photograph of water-immersed filter residue when sodium sulfate is added to water-quenched slag of Panzhihua high-titanium blast furnace slag as a fluxing agent.

FIG. 4 is a Scanning Electron Microscope (SEM) photograph of water-immersed filter residue when sodium bisulfate is added to water-quenched slag of Panzhihua high-titanium blast furnace slag as a fluxing agent.

FIG. 5 is an X-ray diffraction pattern (XRD) of water-immersed filter residue when sodium sulfate is added to water-quenched slag of Panzhihua high-titanium blast furnace slag as a fluxing agent.

FIG. 6 is an X-ray diffraction pattern (XRD) of water-immersed filter residue when the Panzhihua high-titanium blast furnace slag is added with sodium bisulfate as a fluxing agent.

Detailed Description

The invention is further described in the following embodiments, but the content of the invention is not limited to the above, and the titanium-containing blast furnace slag used in the embodiments is high-titanium blast furnace slag water-quenched slag produced by blast furnace smelting of Panzhihua vanadium titano-magnetite. The chemical composition was analyzed by X-ray fluorescence spectroscopy and the results are shown in Table 1.

TABLE 1 high-Ti blast furnace slag water-quenched slag chemical composition table

The high titanium blast furnace slag water-quenched slag is black, has a glossy feeling under light, is loose and has a porous foam structure, is very fragile and fragile, and titanium element is dispersed in various mineral phases. The water quenching slag mainly comprises calcium, titanium, magnesium, aluminum, silicon and other elements to form a five-element slag system, and the extraction and separation of the five-element slag system are important research works in recent years. By adopting an ammonium sulfate salt melting method, magnesium, aluminum, iron, titanium and the like are converted into water-soluble substances, silicon, calcium and the like are converted into water-insoluble substances to achieve the separation purpose, and the enrichment of titanium is realized

Example 1:

(1) drying the high titanium blast furnace slag water-quenched slag in an oven, crushing and grinding the high titanium blast furnace slag water-quenched slag by using a planetary ball mill until the high titanium blast furnace slag water-quenched slag passes through a 200-mesh standard sieve, and obtaining a raw material of the required water-quenched slag.

(2) Accurately weighing 2g of the above water-quenched slag sample passing through 200 meshes, 12g of ammonium sulfate, 2g of sodium sulfate and water-quenched slag: ammonium sulfate: the mass ratio of the sodium sulfate is 1:6:1, and the mixture is placed in a corundum crucible and fully mixed.

(3) And (3) roasting the sample uniformly mixed in the step (2) at 420 ℃ and preserving heat for 60 min.

(4) And (3) after roasting is finished, naturally cooling the sample obtained in the step (2) to room temperature, leaching according to the solid-liquid mass ratio of 1:4, placing the sample in a constant-temperature water bath kettle at 80 ℃, and leaching for 30min under the assistance of mechanical stirring.

(5) And (3) filtering the hot water leaching solution obtained in the step (2), performing vacuum reduced pressure suction filtration to respectively obtain a titanium-rich solution and filter residues, and drying the filter residues for later determination.

(6) And (4) titrating the filtrate obtained in the step (5) by adopting an ammonium ferric sulfate titration method to analyze the content of TiO2 in the sample solution, and calculating to obtain the leaching rate of TiO2 in the high titanium blast furnace slag water-quenched slag, wherein the leaching rate is 97.66%. The chemical composition of the residue was analyzed by X-ray fluorescence spectroscopy as shown in table 2 below.

TABLE 2 chemical composition of water-quenched slag filter residue

Example 2:

(1) drying the high titanium blast furnace slag water-quenched slag in an oven, crushing and grinding the high titanium blast furnace slag water-quenched slag by using a planetary ball mill until the high titanium blast furnace slag water-quenched slag passes through a 200-mesh standard sieve, and obtaining a raw material of the required water-quenched slag.

(2) Accurately weighing 2g of the above water-quenched slag sample passing through 200 meshes, 12g of ammonium sulfate, 5g of sodium bisulfate and water-quenched slag: ammonium sulfate: the mass ratio of the sodium sulfate is 2:12:5, and the mixture is placed in a corundum crucible and fully mixed.

(3) And (3) roasting the sample uniformly mixed in the step (2) at 420 ℃ and preserving heat for 60 min.

(4) And (3) after roasting is finished, naturally cooling the sample obtained in the step (2) to room temperature, leaching according to the solid-to-liquid ratio of 1:4, placing the sample in a constant-temperature water bath kettle at 80 ℃, and reacting for 30min under the assistance of mechanical stirring.

(5) And (3) filtering the hot water leaching solution obtained in the step (2), performing vacuum reduced pressure suction filtration to respectively obtain a titanium-rich solution and filter residues, and drying the filter residues for later determination.

(6) And (4) titrating the filtrate obtained in the step (5) by adopting an ammonium ferric sulfate titration method to analyze the content of TiO2 in the sample solution, and calculating to obtain the leaching rate of TiO2 in the high titanium blast furnace slag water-quenched slag, wherein the leaching rate is 99.65%. The chemical composition of the residue was analyzed by X-ray fluorescence spectroscopy as shown in table 3 below.

TABLE 3 chemical composition of water-quenched slag filter residue