阅读说明：本技术 含钛高炉渣中钛元素的选择性富集长大分离方法 (Selective enrichment, growth and separation method of titanium element in titanium-containing blast furnace slag ) 是由 刘亚东 黄家旭 赵青娥 王东生 于 2019-11-15 设计创作，主要内容包括：本发明公开的是冶金技术领域的一种含钛高炉渣中钛元素的选择性富集长大分离方法,包括以下步骤：将含铁焦炭与含钛高炉渣均匀混合并压块；将块状物料放入加热炉中进行高温处理；取出块状物料进行破碎研磨；对得到的粉末进行磁选,选出的含铁粉料即为富集TiC的精渣。本发明利用TiC晶粒容易在铁粒周围富集长大的特点,预先通过含铁焦炭使含钛高炉渣中95％左右的Ti元素选择性地以TiC的形式在铁粒周围富集长大,得到的Fe-TiC结合体平均粒径可达230μm左右,为进一步进行磁选分离创造了条件,选分后的精渣TiC含量可达25％～30％,Ti元素的回收率可达80％～90％,进而可以有效地增大TiC与氯气接触的机会,促进氯化反应的发生,同时减少反应中氯气的消耗,最终提高氯化效率。(The invention discloses a selective enrichment, growth and separation method of titanium element in titanium-containing blast furnace slag, which belongs to the technical field of metallurgy and comprises the following steps: uniformly mixing iron-containing coke and titanium-containing blast furnace slag and briquetting; putting the block-shaped materials into a heating furnace for high-temperature treatment; taking out the block-shaped materials for crushing and grinding; and carrying out magnetic separation on the obtained powder, wherein the selected iron-containing powder is TiC-enriched refined slag. The invention utilizes the characteristic that TiC crystal grains are easy to enrich and grow around iron grains, about 95 percent of Ti elements in the titanium-containing blast furnace slag are selectively enriched and grown around the iron grains in a TiC form in advance through iron-containing coke, the average grain diameter of the obtained Fe-TiC combination can reach about 230 mu m, conditions are created for further magnetic separation, the TiC content of the selected fine slag can reach 25 to 30 percent, the recovery rate of the Ti elements can reach 80 to 90 percent, the contact chance of TiC and chlorine can be effectively increased, the occurrence of chlorination reaction is promoted, the consumption of chlorine in the reaction is reduced, and the chlorination efficiency is finally improved.)

1. The selective enrichment, growth and separation method of the titanium element in the titanium-containing blast furnace slag is characterized by comprising the following steps:

A. uniformly mixing iron-containing coke and titanium-containing blast furnace slag according to the mass ratio of 1: 2.5-3;

B. briquetting the mixed material;

C. putting the block-shaped materials into a heating furnace for high-temperature treatment, heating to 1400-1600 ℃, then preserving heat, and finally cooling to room temperature;

D. taking out the block-shaped materials, and crushing and grinding the block-shaped materials;

E. and carrying out magnetic separation on the obtained powder, wherein the selected iron-containing powder is TiC-enriched refined slag.

2. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 1, which is characterized in that: the method for preparing the iron-containing coke in the step A comprises the following steps:

a. uniformly mixing and grinding the coking coal and the iron powder according to the mass ratio of 1: 1-1.5;

b. briquetting the ground powder;

c. putting the block-shaped materials into a heating furnace for high-temperature treatment, heating to 1000-1200 ℃, then preserving heat, and cooling to room temperature;

d. and taking out the blocky materials to carry out crushing and grinding to obtain the iron-containing coke powder.

3. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 2, which is characterized in that: in the step a, the mixture particles of the coking coal and the iron powder are ground to 60-80 μm.

4. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 2, which is characterized in that: and c, briquetting the powder in the step b, wherein the pressure is not less than 10 MPa.

5. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 2, which is characterized in that: and c, when high-temperature treatment is carried out in the step c, argon is introduced into the heating furnace for protection, the heating speed and the cooling speed are both 5-10 ℃/min, and the heat preservation time after heating is not less than 2 h.

6. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 2, which is characterized in that: and d, crushing and grinding the blocky materials into iron coke particles with the particle size of 0.3-0.6 mm.

7. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 1, which is characterized in that: in the step A, the grain size of the added titanium-containing blast furnace slag is controlled to be 60-80 μm.

8. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 1, which is characterized in that: and C, when the block material is subjected to high-temperature treatment in the step C, introducing argon into the heating furnace for protection, wherein the heating speed and the cooling speed are both 5-10 ℃/min, and the heat preservation time after heating is not less than 4 h.

9. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 1, which is characterized in that: and D, grinding the blocky materials in the step D until the particle size is less than 200-250 mu m.

10. The method for selective enrichment, growth and separation of titanium element in titanium-bearing blast furnace slag as claimed in claim 1, which is characterized in that: and in the step E, the magnetic field intensity of the magnetic field is controlled to be 150-300 mT.

Technical Field

The invention relates to the technical field of metallurgy, in particular to a selective enrichment, growth and separation method of a titanium element in titanium-containing blast furnace slag.

Background

In order to extract titanium from titanium-containing blast furnace slag, a plurality of research institutions in China carry out related research, and currently, the titanium-containing blast furnace slag is prepared into TiCl through high-temperature carbonization and low-temperature chlorination₄And building materials are one of the most promising technological routes for industrialization. At present, TiCl is prepared by high-temperature carbonization-low-temperature chlorination of titanium-containing blast furnace slag₄And building materials, the phenomenon of coke floating up is serious in the carbonization process, the grade of TiC in the carbide slag finished product is not high, and the particle size of TiC particles is small (only a few to dozens of microns), so that the chlorination efficiency in the low-temperature chlorination process is not high. If the TiC content in the carbide slag finished product can be increased in advance, the reaction efficiency is greatly improved. At present, researches show that a proper amount of Fe is added into the titanium slag of the blast furnace₂O₃The total generation amount of Ti (C, N) is not greatly influenced, but the metallic iron obtained by early reduction can be used as a growth core of Ti (C, N), and can effectively promote the formation and the agglomeration growth of Ti (C, N) grains. But when Fe₂O₃When the addition amount of the titanium (C, N) is increased to 10 percent, the average size of Ti (C, N) crystal grain aggregates can only reach about 7.4 mu m, the grain diameter of the Ti (C, N) crystal grain aggregates can not meet the requirement of mineral separation, and the TiC content in the carbide slag can not be increased.

Disclosure of Invention

In order to overcome the defects of low TiC grade and small particle size in the existing carbide slag finished product, which cause low chlorination efficiency in a low-temperature chlorination process, the invention aims to solve the technical problems that: provides a method for selectively enriching and growing titanium element in the titanium-containing blast furnace slag and separating the titanium element from the blast furnace slag.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the selective enrichment, growth and separation method of titanium element in the titanium-containing blast furnace slag comprises the following steps:

A. uniformly mixing iron-containing coke and titanium-containing blast furnace slag according to the mass ratio of 1: 2.5-3;

B. briquetting the mixed material;

C. putting the block-shaped materials into a heating furnace for high-temperature treatment, heating to 1400-1600 ℃, then preserving heat, and finally cooling to room temperature;

D. taking out the block-shaped materials, and crushing and grinding the block-shaped materials;

E. and carrying out magnetic separation on the obtained powder, wherein the selected iron-containing powder is TiC-enriched refined slag.

Further, the method for preparing the iron-containing coke in the step a comprises the following steps:

a. uniformly mixing and grinding the coking coal and the iron powder according to the mass ratio of 1: 1-1.5;

b. briquetting the ground powder;

c. putting the block-shaped materials into a heating furnace for high-temperature treatment, heating to 1000-1200 ℃, then preserving heat, and cooling to room temperature;

d. and taking out the blocky materials to carry out crushing and grinding to obtain the iron-containing coke powder.

Further, in the step a, the mixture particles of the coking coal and the iron powder are ground to 60-80 μm.

Further, when the powder is briquetted in the step b, the pressure is not less than 10 MPa.

And further, when high-temperature treatment is carried out in the step c, argon is introduced into the heating furnace for protection, the heating speed and the cooling speed are both 5-10 ℃/min, and the heat preservation time after heating is not less than 2 h.

Further, in the step d, the blocky materials are crushed and ground into iron coke particles with the particle size of 0.3-0.6 mm.

Further, in the step A, the grain diameter of the added titanium-containing blast furnace slag is controlled to be 60-80 μm.

And further, when the blocky materials are subjected to high-temperature treatment in the step C, introducing argon into the heating furnace for protection, wherein the heating speed and the cooling speed are both 5-10 ℃/min, and the heat preservation time after heating is not less than 4 h.

Furthermore, when the block material is ground in the step D, the block material needs to be ground until the particle size is less than 200-250 μm.

Furthermore, the magnetic field intensity of the magnetic field in the step E is controlled to be 150-300 mT.

The invention has the beneficial effects that: by utilizing the characteristic that TiC crystal grains are easy to enrich and grow around iron grains, about 95 percent of Ti elements in the titanium-containing blast furnace slag are selectively enriched and grown around the iron grains in a TiC form in advance through iron-containing coke, the average grain diameter of the obtained Fe-TiC combination can reach about 230 mu m, the Fe-TiC combination is far greater than the requirement of mechanical mineral separation, conditions are created for further magnetic separation, the TiC content of the sorted fine slag can reach 25-30 percent, the recovery rate of the Ti elements can reach 80-90 percent, the contact chance of TiC and chlorine can be effectively increased, the occurrence of chlorination reaction is promoted, the consumption of chlorine in the reaction is reduced, and the chlorination efficiency is finally improved.

Drawings

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

Detailed Description

The invention is further illustrated with reference to the following figures and examples.

The process of the selective enrichment, growth and separation method of titanium element in the titanium-containing blast furnace slag is shown in figure 1, and comprises the following steps:

A. uniformly mixing iron-containing coke and titanium-containing blast furnace slag according to the mass ratio of 1: 2.5-3;

B. briquetting the mixed material;

C. putting the block-shaped materials into a heating furnace for high-temperature treatment, heating to 1400-1600 ℃, then preserving heat, and finally cooling to room temperature;

D. taking out the block-shaped materials, and crushing and grinding the block-shaped materials;

E. and carrying out magnetic separation on the obtained powder, wherein the selected iron-containing powder is TiC-enriched refined slag.

The principle of the invention is as follows: at 1400-1600 ℃, only TiO in each component in the titanium-containing blast furnace slag₂The reduction carbonization reaction can be carried out, and TiC crystal grains are easy to enrich and grow around iron grains, so that through specific material proportion and high-temperature treatment, the iron-containing coke is used for reduction carbonization of the titanium-containing blast furnace slag, so that most Ti elements in the slagThe element exists in a TiC form selectively, TiC crystal grains are enriched and grown around iron grains, and the size of the obtained Fe-TiC combination is far larger than the requirement of mechanical beneficiation separation, so that the separation of the Fe-TiC combination in the carbide slag can be realized through magnetic separation.

The iron-containing coke used in the step A can adopt intermediate products in other processes, and can also be prepared in the following mode, and the method specifically comprises the following steps:

a. uniformly mixing and grinding the coking coal and the iron powder according to the mass ratio of 1: 1-1.5;

b. briquetting the ground powder;

c. putting the block-shaped materials into a heating furnace for high-temperature treatment, heating to 1000-1200 ℃, then preserving heat, and cooling to room temperature;

d. and taking out the blocky materials to carry out crushing and grinding to obtain the iron-containing coke powder.

In the step a, preferably, the mixture particles of the coke coal and the iron powder are ground to 60-80 μm, so that the contact area is increased, the reaction efficiency is improved, the ratio of the coke coal to the iron powder can enable the carbonization reaction to be sufficient, about 95% of Ti elements in the blast furnace slag are selectively enriched and grown around iron particles in a TiC form, and the Fe-TiC combination is obtained. And (c) briquetting the powder in the step (b), wherein the pressure is preferably not less than 10MPa, so that the coking coal and the iron powder form compact iron-containing coke to support the subsequent crushing into iron coke particles. And c, when high-temperature treatment is carried out in the step c, argon is introduced into the heating furnace for protection, so that the reaction of the iron powder and the coke with air is avoided, the flow of argon is about 1L/min, the heating speed and the cooling speed are preferably controlled to be 5-10 ℃/min, the heat preservation time after heating is not less than 2h, and the formation of the iron-containing coke is facilitated. And finally, in the step d, preferably crushing and grinding the blocky materials into iron coke particles with the particle size of 0.3-0.6 mm, so as to facilitate the subsequent mixing reaction with the blast furnace slag.

When the iron-containing coke and the titanium-containing blast furnace slag are used for carbonization reaction, the following process parameters are required to be controlled: in the step A, the grain size of the added titanium-containing blast furnace slag is preferably controlled to be 60-80 μm, so that the titanium-containing blast furnace slag can be conveniently and fully contacted and reacted with the iron-containing coke. And C, when the blocky materials are subjected to high-temperature treatment in the step C, introducing argon into the heating furnace for protection, so as to avoid the reaction of air and the iron-containing coke, wherein the flow of the argon is about 1L/min. The heating rate and the cooling rate are both 5-10 ℃/min, the heat preservation time after heating is not less than 4h, and the carbonization reaction and the selective enrichment and growth of Ti element around iron grains in a TiC form are facilitated. And finally, in order to meet the subsequent magnetic separation requirement, when the blocky material is ground in the step D, the blocky material needs to be ground until the grain diameter is less than 200-250 mu m and is equivalent to the average grain diameter of the Fe-TiC combination body about 230 mu m.

Finally, during magnetic separation, the magnetic field intensity of the magnetic field is preferably controlled to be 150-300 mT, the content of TiC in the fine slag obtained through separation can reach about 25%, and the recovery rate of Ti element reaches 80-90%. Too much impurities can be absorbed due to too high magnetic field strength, so that the recovery rate of the Ti element is reduced.

This is further illustrated by the following examples.

The invention is implemented by taking titanium-containing blast furnace slag of a certain steel plant as a raw material, and the components are shown in the following table 1:

TABLE 1 Main component (wt%) of titanium-containing blast furnace slag

Constituent elements	CaO	SiO2	MgO	Al2O3	TiO2	FeO	V2O5	K2O	Na2O	MFe
											Content (wt.)	28.16	25.58	6.67	13.02	22.55	0.90	0.27	0.68	0.41	＜0.5