阅读说明：本技术 人造金红石母液的处理方法 (Method for treating artificial rutile mother liquor ) 是由 陈洪 李露 杨洪武 冯支斌 于 2020-05-26 设计创作，主要内容包括：本发明公开了一种人造金红石母液的处理方法,将还原钛加入人造金红石母液中进行浸出反应,反应结束后固液分离得母液和固相物,所述固相物进行煅烧得人造金红石,所得母液中酸浓度＜3％；所述浸出温度为50～120℃,所述浸出反应时间为2～8h；所述还原钛与人造金红石母液的质量：体积比(g：mL)为1﹕4～7,所述还原钛中铁的金属化率60％～90％,所述人造金红石母液中酸质量浓度为8～12％。本发明采用还原钛处理人造金红石母液,处理后母液中残酸量低于3％,提高了盐酸的利用率,增加了金红石产量,母液中铁浓度提高,为后续母液的处理降低了能耗和处理难度。(The invention discloses a method for treating artificial rutile mother liquor, which comprises the steps of adding reduced titanium into the artificial rutile mother liquor to carry out leaching reaction, carrying out solid-liquid separation after the reaction is finished to obtain mother liquor and a solid phase substance, calcining the solid phase substance to obtain artificial rutile, wherein the acid concentration in the obtained mother liquor is less than 3%; the leaching temperature is 50-120 ℃, and the leaching reaction time is 2-8 h; the mass of the reduced titanium and the synthetic rutile mother liquor is as follows: the volume ratio (g: mL) is 1: 4-7, the metallization rate of iron in the reduced titanium is 60% -90%, and the acid mass concentration in the artificial rutile mother liquor is 8-12%. The invention adopts reduced titanium to treat the artificial rutile mother liquor, the residual acid content in the treated mother liquor is lower than 3 percent, the utilization rate of hydrochloric acid is improved, the rutile yield is increased, the iron concentration in the mother liquor is improved, and the energy consumption and the treatment difficulty are reduced for the subsequent treatment of the mother liquor.)

1. The treatment method of the artificial rutile mother liquor is characterized by comprising the following steps: adding reduced titanium into the artificial rutile mother liquor to carry out leaching reaction, carrying out solid-liquid separation after the reaction is finished to obtain mother liquor and a solid phase, and calcining the solid phase to obtain the artificial rutile, wherein the acid concentration in the obtained mother liquor is less than 3%;

the leaching temperature is 50-120 ℃, and the leaching reaction time is 2-8 h;

the mass of the reduced titanium and the synthetic rutile mother liquor is as follows: the volume (g: mL) is 1: 4-7, the metallization rate of iron in the reduced titanium is 60% -90%, and the acid mass concentration in the artificial rutile mother liquor is 8-12%.

2. The process for treating an artificial rutile mother liquor as claimed in claim 1, wherein: the leaching reaction comprises low-temperature leaching and high-temperature leaching, wherein the low-temperature leaching temperature is 50-90 ℃, the high-temperature leaching is carried out when no small bubbles are generated in reactants in the leaching reaction process, and the high-temperature leaching temperature is 90-120 ℃.

3. The process for treating an artificial rutile mother liquor as claimed in claim 1 or 2, wherein: the acid in the synthetic rutile mother liquor is hydrochloric acid.

4. The process for treating an artificial rutile mother liquor as claimed in claim 1 or 2, wherein: the preparation method of the reduced titanium comprises the following steps: mixing the titanium concentrate and the coal powder, adding the mixture into a rotary kiln for reduction reaction at the temperature of 1200-1400 ℃, and cooling the reduced material under the protective atmosphere condition to obtain reduced titanium.

5. The process for treating an artificial rutile mother liquor as claimed in claim 1 or 2, wherein: the concentration of the iron element in the artificial rutile mother liquor is 80-140 g/L.

Technical Field

The invention relates to a waste liquid treatment method in the chemical field, in particular to a treatment method of artificial rutile mother liquor.

Background

The artificial rutile is an important basic raw material for titanium industry, is mainly used for producing titanium dioxide, titanium sponge, titanium tetrachloride and welding electrode coatings by chlorination process, and is an excellent substitute product of natural rutile. Among different production process routes of the artificial rutile, the production process of the artificial rutile by the hydrochloric acid method has the advantages of high leaching speed, strong impurity removal capability, high product quality, suitability for treating various mineral sources and the like, becomes a mainstream process, and realizes industrialization very early.

In the world, more than 20 enrichment methods have been researched and proposed for the research on the enrichment method of titanium concentrate, and each treatment method has unique characteristics. But can be roughly classified into two types-dry and wet. The dry method comprises an electric furnace smelting method, a plasma smelting method, a selective chlorination method and other thermal reduction methods; the wet method comprises a partial reduction-hydrochloric acid leaching method and a partial reduction-sulfuric acid leaching method (which is generally called acid leaching method), a full reduction-corrosion method and a full reduction-FeCl₃Leaching, and other chemical separation processes. The acid leaching method is the most effective method for removing impurities, and can effectively remove impurity iron and most of CaO, MgO and Al₂O₃MnO and other impurities to obtain TiO₂The artificial rutile with higher mass fraction can be applied to all titanium concentrates in the world due to the best leaching effect of acid in the hydrochloric acid method, and can realize the regeneration, recovery and cyclic utilization of hydrochloric acid, but equipment needs to be made of special anticorrosive materials, the waste acid treatment energy consumption is high, and a cheap energy medium is needed to be selected for treatment.

In the production process of the synthetic rutile by the hydrochloric acid method, about 22-31% of hydrochloric acid is generally adopted to carry out acid leaching on the titanium concentrate after oxidation-reduction modification, and iron oxide and most of CaO, MgO and Al in the titanium concentrate are selectively leached₂O₃And the impurities are mixed, and then the TiO-containing material is finally obtained through the procedures of washing, calcining, magnetic separation and the like₂High-grade artificial rutile with the content of 90-96 percent. The hydrochloric acid is used for leaching the titanium concentrate, so that iron, most of CaO, MgO and Al in the titanium concentrate can be effectively removed₂O₃MnO and other impurities, and the production process for preparing the artificial rutile by the hydrochloric acid leaching method has high leaching speedStrong impurity removal capability, high product grade and the like, thereby being particularly suitable for treating various types of titanium concentrates. However, in the process of manufacturing the artificial rutile by leaching the titanium concentrate with hydrochloric acid, iron-containing substances, calcium-magnesium oxides and the like in the titanium concentrate are dissolved to form chloride, and the chloride enters the solution to form artificial rutile mother liquor, 5-7 t of artificial rutile mother liquor is generated for producing 1 ton rutile products on average, and the artificial rutile mother liquor contains various metal chlorides and ferric chloride and also contains part of unreacted hydrochloric acid, so that the artificial rutile is difficult to recycle. The typical composition of the synthetic rutile mother liquor is shown in the following table:

composition (I)	FeCl2+FeCl3	HCl	AlCl3	CaCl2	MgCl2	TiOCl2	MnO	Mechanical impurities	Moisture content	Others
											Content/%	23.41	10.2	1.35	0.86	2.52	5.45	1.21	0.52	55	0.69

The national "sixty-five" and "seventy" have studied a lot on the comprehensive utilization and treatment of the mother liquor of artificial rutile leaching, such as utilizing the mother liquor of acid leaching to introduce chlorine oxide to prepare liquid ferric trichloride, preparing iron powder by salting out crystallization, treating the mother liquor to produce iron red and brine by a combination method, etc., but because its technology has high energy consumption or does not utilize the residual acid in the mother liquor of rutile effectively, there is also technology to recycle hydrochloric acid in the mother liquor of rutile at present, but because of the limit of hydrochloric acid regeneration, the hydrochloric acid concentration after regeneration is low, unfavorable to recycle and leach, the iron content in the mother liquor of leached rutile is low at the same time, the energy consumption of acid regeneration treatment is high, the cost is high, influence the economic benefits of rutile production.

Chinese patent application publication No. CN 1657426a discloses a method for recovering and treating artificial rutile mother liquor, which comprises heating and concentrating the artificial rutile mother liquor to increase the concentration of ferric chloride, spraying into a roasting furnace for roasting, carrying out thermal decomposition reaction on ferric chloride under high-temperature oxidation atmosphere to form hydrogen chloride gas and solid oxide mainly containing ferric oxide, and absorbing the hydrogen chloride gas with water to obtain regenerated hydrochloric acid. Although the method realizes the recycling of chloride ions, the energy consumption is high, about 640 ten thousand calories of heat are required for processing mother liquor generated by one ton of synthetic rutile, and the energy consumption is reduced to 800Nm of natural gas³About 70% of the heat in the treatment modeConsuming on the latent heat of evaporation of water. Patents with publication numbers CN103159263A, CN104528834A, CN105110784A, etc. all adopt a concentration and crystallization technology to separate and obtain relatively pure ferrous chloride, which is then used as a raw material to perform calcination or chemical treatment to obtain iron oxide red or ferrite by-products with relatively high value, so as to offset the comprehensive treatment cost of the synthetic rutile mother liquor. In order to ensure the leaching efficiency in the production process of the artificial rutile, the mineral acid ratio is generally maintained at 1: 3-1: 3.5 (22% -26% hydrochloric acid), the theoretical excess of hydrochloric acid is over 50%, so that the mother liquor contains a large amount of residual acid and the concentration of iron ions is low, a large amount of residual acid needs to be evaporated during crystallization separation, in order to improve the crystallization efficiency, the refrigeration treatment is also needed, a large amount of energy is consumed in the processes, the treatment cost is increased, and the excess hydrochloric acid is not effectively utilized, so that the production cost is improved. It can be seen that, in the current treatment of the artificial rutile mother liquor, the hydrochloric acid and iron elements in the mother liquor are concentrated to be recovered, the rutile mother liquor is also used for pretreating modified titanium concentrate, the treated modified titanium concentrate is subjected to acid leaching, the concentration of the hydrochloric acid in the mother liquor after the modified titanium concentrate is reduced from about 10% to about 6-8%, and the mother liquor is difficult to react with the titanium concentrate, so that the residual acid is still not effectively recovered and utilized.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for treating artificial rutile mother liquor, which utilizes residual acid in the artificial rutile mother liquor to prepare a qualified titanium-rich material.

The technical scheme adopted by the invention for solving the technical problems is as follows: the method for treating the artificial rutile mother liquor comprises the steps of adding reduced titanium into the artificial rutile mother liquor to carry out leaching reaction, carrying out solid-liquid separation after the reaction is finished to obtain mother liquor and a solid phase substance, calcining the solid phase substance to obtain the artificial rutile, wherein the acid concentration in the obtained mother liquor is less than 3%;

the leaching temperature is 50-120 ℃, and the leaching reaction time is 2-8 h;

the mass of the reduced titanium and the synthetic rutile mother liquor is as follows: the volume (g: mL) is 1: 4-7, the metallization rate of iron in the reduced titanium is 60% -90%, and the acid mass concentration in the artificial rutile mother liquor is 8-12%.

At present, two methods are mainly used for treating residual acid in the artificial rutile mother solution, namely, hydrogen chloride in the artificial rutile mother solution is recycled through regeneration, titanium concentrate is pretreated by using the residual acid in the artificial rutile mother solution, and then a titanium-rich material is obtained through acid leaching by using new acid, so that the energy consumption is large, the cost is high, and the economic benefit is low if hydrochloric acid is recycled through regeneration; if the titanium concentrate is pretreated by using the residual acid in the artificial rutile mother liquor, the concentration of the residual acid after reaction can only be reduced to 6-8%, the utilization rate of the residual acid in the mother liquor is low, the recycling still needs to pay large cost, the pretreated titanium concentrate needs further acid leaching to obtain a qualified titanium-rich material, and people cannot imagine that qualified artificial rutile can be obtained by using the residual acid due to the low concentration and high impurity content of the acid in the artificial rutile mother liquor. The invention selects the reduced titanium as the treating agent, adjusts the mineral acid ratio and the existence form of the iron element in the reduced titanium, not only reduces the concentration of the residual acid in the mother solution to be below 3 percent, but also directly obtains the high-grade titanium-rich material without other treatments, greatly improves the economic benefit of titanium dioxide production, and can be popularized and applied in industrial production.

Further, the leaching reaction comprises low-temperature leaching and high-temperature leaching, the low-temperature leaching temperature is 50-90 ℃, the high-temperature leaching is carried out when no small bubbles are generated in reactants in the leaching reaction process, and the high-temperature leaching temperature is 90-120 ℃.

Further, the acid in the synthetic rutile mother liquor is hydrochloric acid.

Further, the preparation method of the reduced titanium comprises the following steps: mixing the titanium concentrate and the coal powder, adding the mixture into a rotary kiln for reduction reaction at the temperature of 1200-1400 ℃, and cooling the reduced material under the protective atmosphere condition to obtain reduced titanium.

Further, the concentration of the iron element in the artificial rutile mother liquor is 80-140 g/L.

The invention has the beneficial effects that: the invention adopts reduced titanium to treat the artificial rutile mother liquor, the residual acid content in the treated mother liquor is lower than 3 percent, the utilization rate of hydrochloric acid is improved, the rutile yield is increased, the iron concentration in the mother liquor is improved, and the energy consumption and the treatment difficulty are reduced for the subsequent treatment of the mother liquor;

the content of titanium dioxide in the prepared artificial rutile is more than 90.36%, the titanium recovery rate is more than 95.9%, no new waste liquid is generated in the reaction process, the obtained leached solid is a qualified titanium-rich material without adopting neo-acid leaching, the production cost and the environmental protection treatment cost of titanium dioxide are greatly reduced, and considerable economic benefit is brought.

Detailed Description

The present invention will be further described with reference to the following examples.