CN109055781B - Method for preparing titanium product by taking ferrotitanium composite ore as raw material - Google Patents
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- C22B34/1222—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using a halogen containing agent
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Abstract
The invention relates to a method for preparing a titanium product by taking a ferrotitanium composite ore as a raw material, belonging to the field of chemical industry. The preparation method comprises the following steps: the ferrotitanium composite ore raw material is mixed with carbon raw material according to a certain stoichiometric ratio, and then heated and reduced under a certain atmosphere, so that the iron component is reduced into metallic iron, the titanium component is converted into titanium oxycarbide and titanium oxycarbonitride, and other components (aluminum, magnesium, calcium and silicon) are kept in an oxide state. After the iron component is separated, the slag phase is selectively chlorinated at low temperature, and titanium tetrachloride with the grade higher than 99 percent can be directly obtained. The method can effectively reduce the cost of the existing method for extracting iron and titanium, effectively solve the problem that other oxides are simultaneously chlorinated in the existing chlorination method, obviously enhance the selectivity of the chlorination procedure in the production process of titanium tetrachloride, improve the chlorination efficiency of titanium, directly obtain highly purified titanium products, do not need subsequent refining and purification, and greatly simplify the method flow for extracting iron and titanium elements from the titanic iron composite ore.
Description
Technical Field
The invention mainly belongs to the technical field of chemical industry, relates to a method for preparing a titanium product by taking a ferrotitanium composite ore as a raw material, and particularly relates to a method for preparing titanium tetrachloride and titanium dioxide by taking the ferrotitanium composite ore as a raw material. The method is characterized in that iron components in the ferrotitanium composite ore are converted into metallic iron by accurately controlling high-temperature carbothermic reduction, titanium components are converted into titanium oxycarbide, titanium oxycarbonitride and other oxides to form a mixture which is used as a chlorination raw material, and highly purified titanium tetrachloride can be directly obtained through chlorination treatment; titanium tetrachloride is oxidized to obtain highly purified titanium dioxide.
Background
The ferrotitanium composite ore, such as vanadium titano-magnetite in Panxi area and Hebei Chengde area of China, has wide distribution, rich reserves and huge resources, and the titanium resource accounts for more than 91 percent of the national titanium resource, thus having extremely high comprehensive utilization value. The basic process route of the process is to reduce iron and vanadium oxides in minerals into vanadium-containing molten iron, and titanium components mainly enter slag in the form of low-valence oxides. Due to the difference of furnace burden and smelting technology level, the slag iron ratio is relatively high, a large amount of titanium slag is difficult to effectively treat, most of the titanium slag is processed into building material materials with low economic value, such as granulated slag, slag macadam, expanded slag, slag bead and the like, the titanium component in the building material materials cannot be effectively utilized, and the huge waste is caused to abundant titanium resources in China.
Aiming at the partial titanium-containing slag, the process of high-temperature carbonization-low-temperature chlorination in the prior art reduces the titanium component in the titanium-containing slag into titanium carbide through the high-temperature carbonization process, and utilizes titanium carbide (TiC) and gangue component (Al)2O3、MgO、CaO、SiO2) The chlorination selectivity of the method is that the carbonized slag is subjected to low-temperature chlorination treatment to prepare titanium tetrachloride, so that the recovery and utilization of titanium components in the titanium-iron composite ore are realized. However, since this process controls the end point of the carbonization-reduction at titanium carbide (TiC), carbon generated during the chlorination reaction promotes the gangue component (Al) in a reducing manner2O3、MgO、CaO、SiO2) The chlorination obviously reduces the selectivity of the chlorination process, and further leads the prepared titanium tetrachloride to contain a certain amount of chlorinated impurities (AlCl)3、MgCl2、CaCl2、SiCl4) The titanium tetrachloride with higher purity can be obtained only by secondary treatment with subsequent refining procedure and recovery procedure. The unnecessary waste of the original auxiliary materials is brought, the titanium chlorination efficiency is reduced, the process flow is lengthened, the process difficulty is increased, and the process economic cost is improved. Obviously, the process for preparing titanium tetrachloride by using the ferrotitanium composite ore in the prior art needs to be further improved.
Meanwhile, in the process of producing titanium products by using titanium-rich phase substances containing carbon (nitrogen) titanium oxide generated after preparing iron by adopting other ferrotitanium raw materials in the prior art, the fact that specific components of the carbon (nitrogen) titanium oxide have various possibilities due to different process conditions is found, and more gangue components are chlorinated under partial conditions, so that the purity of the obtained titanium products is different, and if the titanium products are applied to the industry, certain post-treatment is still required to be carried out on the titanium products which do not meet the purity requirement, so that the problem of quality stability of the produced titanium products is not fundamentally solved.
Disclosure of Invention
In view of the above-mentioned technical problems,the invention provides a method for preparing a titanium product by taking a ferrotitanium composite ore as a raw material, which can effectively solve the problem that part of gangue component (Al) is generated in the process of producing titanium tetrachloride by utilizing the ferrotitanium composite ore2O3、MgO、CaO、SiO2) Meanwhile, the chlorination causes the problem of more impurities in the product, the pressure of the subsequent refining and impurity removing process is greatly relieved, the chlorination efficiency of the titanium component is effectively improved, the resource consumption and the process cost are reduced, and the utilization rate of the titanium resource in the ferrotitanium composite ore is obviously improved.
The invention is realized by the following technical scheme:
a method for preparing a titanium product by taking a ferrotitanium composite ore as a raw material, which comprises the following steps:
(1) carrying out crushing pretreatment on a ferrotitanium composite ore raw material;
(2) adding a carbon-containing reducing agent into the crushed and pretreated raw materials to obtain a mixture;
(3) heating the mixture under a certain atmosphere to carry out reduction reaction to obtain a reduction product containing titanium-rich phase substances, iron and slag phase components;
(4) discharging and separating iron in the reduction product to obtain a primary product containing a titanium-rich phase substance and a slag phase component;
(5) and (3) taking the primary product as a chlorination raw material, placing the chlorination raw material in chlorination equipment, selectively chlorinating at a certain temperature, keeping a slag phase component in a solid state of an oxide in the selective chlorination process, chlorinating the titanium-rich phase substance to generate titanium tetrachloride vapor, condensing and collecting to obtain a titanium tetrachloride product with the purity higher than 99%.
Further, the titanium-rich phase substance includes titanium oxycarbide TiCmOnAnd titanium oxycarbonitride TiCxNyOzAt least one of;
the titanium oxycarbide TiCmOnWherein m + n is 1 and m/n is 0.5-1;
TiC of titanium oxycarbonitridexNyOzWherein x + y + z is 1, y is more than 0 and less than or equal to 1, and x/z is more than or equal to 0.5 and less than or equal to 1.
Further, the amount of carbonaceous reducing agent dosed in step (2) is such as to reduce all of the iron oxides in the ilmenite composite ore feedstock to metallic iron and all of the titanium oxides in the ilmenite composite ore feedstock to titanium oxycarbide or titanium oxycarbonitride or a mixture of both.
Further, in the step (3), after the temperature rise process reaches the set temperature, the temperature is kept for a period of time.
Further, the heat preservation period is 2-10 hours.
Further, in the step (3), the temperature is raised to 1100-2200 ℃ for reduction reaction.
Further, in the step (3), the temperature is raised to 1100-1400 ℃ for reduction reaction.
Further, the atmosphere in the step (3) includes an argon, nitrogen or air atmosphere.
Further, after the step (2) and before the step (3), the steps of ball milling, uniformly mixing and compression molding the mixture are also included.
Further, in the step (4), the method for discharging and separating the iron in the reduction product comprises the following steps: directly discharging reduced molten iron at high temperature after the reduction reaction; or removing iron in the reduction product by adopting a solid iron reselection and magnetic separation mode.
Further, when a solid iron reselection and magnetic separation mode is adopted, the method also comprises the step of pretreating the reduction product before discharging and separating iron, and the step of pretreating the reduction product comprises the dispersion treatment of crushing, ultrasonic treatment and ball milling.
Further, when a magnetic separation mode of solid iron is adopted, the reduction product is pretreated to obtain a magnetic separation raw material, and the magnetic separation raw material is placed in magnetic separation equipment for magnetic separation.
Further, in step (5), the temperature at which the selective chlorination is carried out is: 200 to 600 ℃.
Further, the ilmenite composite ore comprises any one of ilmenite, vanadium-titanium magnetite ore, titanium concentrate, iron concentrate, high-titanium slag and rutile or a combination of any two or more of the ilmenite ore, the vanadium-titanium magnetite ore, the titanium concentrate, the iron concentrate and the rutile.
Further, the carbonaceous reducing agent comprises any one or a combination of any two or more of activated carbon, graphite powder, charcoal, petroleum coke, asphalt, coke powder and coal powder.
A method for preparing titanium dioxide, which takes the titanium tetrachloride prepared by any one of the methods in claims 1-15 as a raw material and prepares the titanium dioxide through oxidation treatment.
Different from the prior art that titanium carbide (TiC) is taken as a main chlorination object, carbon is generated after chlorination so as to reduce and chlorinate other oxides (Al)2O3MgO, CaO and SiO2) Resulting in impure products. The method provided by the invention accurately controls the carbothermic reduction process of the ferrotitanium composite ore to a specific degree, namely, iron oxide in the raw material is completely reduced into metallic iron, and titanium oxide is completely reduced into titanium oxycarbide TiCmOnAnd/or titanium oxycarbonitride TiCxNyOz(ii) a And precisely controlling the carbon-to-oxygen ratio (TiC of said titanium oxycarbide)mOnWherein m + n is 1 and m/n is 0.5-1; TiC of titanium oxycarbonitridexNyOzWherein x + y + z is 1, y is more than 0 and less than or equal to 1, and x/z is more than or equal to 0.5 and less than or equal to 1), so that all carbon elements and titanium oxycarbide TiCmOnAnd/or titanium oxycarbonitride TiCxNyOzThe oxygen element in the (C) is discharged to form carbon oxide gas without generating any other oxide (Al) promoting2O3MgO, CaO and SiO2) Carbon generated by chlorination reaction, thereby avoiding other oxides (Al) in the subsequent chlorination procedure2O3MgO, CaO and SiO2) The chlorination reaction of (2) improves the selectivity of the chlorination process.
Therefore, the method provided by the invention not only obviously reduces the burden of the subsequent refining and impurity removal process, avoids unnecessary consumption of raw and auxiliary materials in the existing titanium tetrachloride production process, improves the chlorination efficiency of titanium, reduces the process economic cost, but also provides a simpler, more convenient and more effective way for producing titanium tetrachloride and titanium white chloride from low-grade titanium raw materials: in particular, in the case of passing through blast furnaces, electric furnaces, or the likeAfter the precise control reduction of iron and titanium components and the discharge of iron components in the titanic-iron composite ore are completed, TiC containing titanium oxycarbidemOnAnd/or titanium oxycarbonitride TiCxNyOz(ii) a (the titanium oxycarbide TiCmOnWherein m + n is 1 and m/n is 0.5-1; TiC of titanium oxycarbonitridexNyOzIn the method, the slag with x + y + z being 1, y being more than 0 and less than or equal to 1 and x/z being more than or equal to 0.5 and less than or equal to 1) is subjected to low-temperature selective chlorination, so that titanium tetrachloride products with the grade as high as 99% can be directly obtained, secondary refining and purification steps are not needed, the implementation process is obviously different from the scheme in the prior art, the problem that high-purity titanium products cannot be directly obtained by the preparation processes of various titanium products is solved, and the technical effect is obviously superior to that of the prior art; the titanium tetrachloride product is used as a raw material, and highly purified titanium dioxide can be prepared after oxidation treatment, so that the preparation process of the titanium product is greatly simplified, and the provided titanium product has high purity, high quality and high competitiveness.
In addition, the invention simplifies, efficiently and smoothly prepares the iron and titanium products from the ferrotitanium paragenetic ore, eliminates the problems of redundancy and complexity in the prior preparation process, and titanium element entering slag or being dumped or processed in a complex and low-efficiency process mode due to the fact that the extraction and utilization of the iron element are only emphasized, so that the potential value is not fully exerted, and is beneficial to fully utilizing mineral resources and social resources.
The invention has the beneficial technical effects that:
1) the method comprises the steps of mixing the raw material of the ferrotitanium composite ore with the carbon raw material according to a certain stoichiometric ratio, heating and reducing under a certain atmosphere to reduce the iron component into metallic iron, converting the titanium component into titanium oxycarbide and titanium oxycarbonitride, and keeping other components (aluminum, magnesium, calcium and silicon) in an oxide state; by accurately controlling the production method of the ferrotitanium composite ore, a titanium-rich phase substance which is different from the prior art and has specific components is obtained, the titanium-rich phase substance is taken as a chlorination raw material, so that the selectivity of a chlorination procedure in the prior art is greatly improved, the chlorination efficiency of titanium is improved, a titanium product with stable quality and high purification is obtained, the process flow is simplified, and the resource consumption is reduced;
2) the method provided by the invention provides a plurality of iron component separation modes, so that the flexibility and the economy of the process are enhanced;
3) the method disclosed by the invention fully utilizes the iron and titanium components in the raw materials, and has the advantages of simple and compact flow, stable process parameters, low production cost, environmental friendliness, energy conservation and environmental friendliness;
4) the method has strong raw material applicability, and can be widely applied to various grades of ferrotitanium composite ores.
5) The method can effectively reduce the process cost of extracting iron and titanium, effectively solve the problem that other oxides are chlorinated simultaneously in the conventional chlorination process, obviously enhance the selectivity of the chlorination process in the production process of titanium tetrachloride, improve the chlorination efficiency of titanium, directly obtain highly purified titanium products, do not need subsequent refining and purification, and greatly simplify the process flow of extracting iron and titanium elements from the titanic iron composite ore.
Drawings
FIG. 1 is a flow chart of a method for preparing titanium tetrachloride by using a titanic iron composite ore as a raw material;
FIG. 2 is an X-ray diffraction pattern of the lower part of a reduced product in an argon atmosphere according to example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of the upper part of a reduction product in an argon atmosphere according to example 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern of the low temperature chlorination residue of example 1 of the present invention;
FIG. 5 is an X-ray diffraction pattern of an oxidation product of example 1 of the present invention;
FIG. 6 is an X-ray diffraction pattern of the upper part of a reduced product in an argon atmosphere according to comparative example 1 of the present invention;
FIG. 7 is an X-ray diffraction pattern of a low temperature chlorination residue of comparative example 1 of the present invention;
FIG. 8 is an X-ray diffraction pattern of the upper part of a reduced product in an argon atmosphere according to comparative example 2 of the present invention;
FIG. 9 is an X-ray diffraction pattern of the low temperature chlorination residue of comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
The ilmenite is a general term of a kind of ores, and contains various titanium and iron-rich ores such as vanadium-titanium magnetite in Panxi and Chengde areas of China, and specifically comprises at least one ore of ilmenite, vanadium-titanium magnetite, titanium concentrate, iron concentrate, high-titanium slag, rutile and the like.
The method can be carried out in equipment such as Raymond mill, etc. the method can be used for carrying out pretreatment such as crushing on the ferrotitanium composite ore to increase the surface area of the ore, is favorable for contacting with a reducing agent and ensures full reaction.
After a carbonaceous reducing agent is added into the mineral powder, the mixture is ball-milled and mixed evenly, and the powder is pressed and formed;
the carbonaceous reducing agent specifically comprises at least one of activated carbon, graphite powder, charcoal, petroleum coke, asphalt, coke powder, coal powder and the like;
the amount of the carbonaceous reducing agent is calculated according to the stoichiometric ratio of the chemical reaction, so that the carbothermic reduction process is controlled to be carried out to a proper extent, and iron oxide in the raw material is completely reduced to metallic iron, and titanium oxide is completely reduced to titanium oxycarbide, titanium oxycarbonitride or a mixture of the two;
heating the mixture in a device such as a blast furnace or an electric furnace and the like under a certain atmosphere to perform high-temperature reduction reaction, wherein the atmosphere can be any one of argon, nitrogen, air or a mixture thereof; wherein the temperature rise process is as follows: slowly raising the temperature to about 1100-2200 ℃, and preferably 1100-1400 ℃; preserving heat for a period of time after the set temperature is reached, wherein the heat preservation time is different from 1 to 15 hours according to the situation, and is more preferably 2 to 10 hours;
through high-temperature reduction reaction, iron oxide in the ferrotitanium composite ore raw material is completely reduced into metallic iron, and titanium oxide is completely reduced into titanium oxycarbide, titanium oxycarbonitride or a mixture of the titanium oxycarbonitride and the titanium oxycarbonitride;
removing iron in the obtained reduction product, and after the reduction product is pretreated by the working procedures such as cooling, crushing, wet grinding, refining and the like, placing the humidified powder in magnetic separation equipment for magnetic separation to fully remove iron phase components in the humidified powder, wherein the magnetic separation equipment can adopt annular energy to process circulating flow raw materials; or directly discharging the reduced molten iron at a high temperature after the reduction reaction. Both modes finally obtain a titanium-rich phase substance and a slag phase component (Al)2O3MgO, CaO and SiO2) The primary separation product of (1);
placing the primary product as a chlorination raw material in chlorination equipment, performing selective chlorination at 200-600 ℃, chlorinating a titanium-rich phase substance into titanium tetrachloride vapor, condensing and collecting the titanium tetrachloride vapor to obtain a titanium tetrachloride product with the purity higher than 99%, wherein a slag phase component is kept in a solid state of an oxide;
the titanium tetrachloride product obtained can be oxidized to obtain titanium dioxide, and can also be used as a raw material for producing metallic titanium.
The following detailed examples and comparative examples are intended to better illustrate the specific efficacy or features of the inventive technology disclosed above, and in accordance with well-known conventions, the scope of the subject matter of the present patent disclosure is not limited only to the process parameters and conditions provided in the following examples.
Example 1
200.0g of ilmenite (FeO: 42.7%, TiO) crushed into fine particles by a vibration mill was weighed2: 47.5 percent), adding 42.9g of graphite powder (with the carbon content of 99.9 percent), placing the mixture into a planetary ball mill, uniformly mixing, performing compression molding on the powder after ball milling, placing the powder into a high-temperature furnace, and controlling the argon in the furnaceSlowly raising the temperature to 2000 ℃ in the atmosphere, preserving the heat for 3 hours, and then cooling to room temperature to obtain a reduction product divided into an upper part and a lower part, wherein the lower part is analyzed for the structure through X-ray diffraction, and the reduction product is iron as shown in the attached figure 2 of the specification; the upper part is analyzed by X-ray diffraction to obtain a structure shown in figure 3 of the specification, which is titanium oxycarbide (TiC)0.5O0.5X/z ═ 1) with other unreduced oxide components. It can be seen that after carbothermic selective reduction, the iron oxide in the ilmenite was reduced to metallic iron and deposited on the lower part, and the titanium oxide was reduced to titanium oxycarbide (TiC)0.5O0.5) And other oxide component (Al)2O3-MgO-CaO-SiO2) At the upper part. Crushing and grinding the upper block of the reduction product to below 200 meshes, performing chlorination treatment at 200 ℃, performing X-ray diffraction analysis on the residue after the reaction is completed, and obtaining the result shown in the attached figure 4 of the specification, wherein the result is other oxide components (Al)2O3-MgO-CaO-SiO2) (ii) a After the chlorination product is further oxidized, the obtained oxidized product is analyzed by X-ray diffraction, and the result is shown in figure 5 in the specification and is titanium dioxide (TiO)2) The compositional analysis showed that the purity was 99.4%, indicating that the titanium component in the ilmenite composite was reduced to titanium (nitrogen) oxide (TiC)x(Ny)Oz) Then chlorination treatment is carried out, so that selective chlorination between the titanium component and other oxide components can be realized, and highly purified titanium tetrachloride and titanium dioxide can be obtained finally.
Example 2:
200.0g of high titanium slag (Fe) crushed into fine particles by a vibration mill is weighed2O3：10.5％，TiO2: 77.7 percent of graphite powder (with carbon content of 99.9 percent) of 48.1g is added, the mixture is placed in a planetary ball mill to be uniformly mixed, the powder after ball milling is pressed and molded and is placed in a high-temperature furnace, the temperature in the furnace is controlled to be in nitrogen atmosphere and is slowly raised to 1300 ℃, the temperature is kept for 7 hours and then is cooled to room temperature, a reduction product divided into an upper part and a lower part is obtained, iron is deposited on the lower part of the reduction product, and the structure of the upper part is analyzed by X-ray diffraction, and the reduction productxNyOzX/z ═ 0.75) with unreduced componentsAnd (3) mixing. Crushing and grinding the upper block of the reduction product to below 200 meshes, chlorinating at 400 ℃, and carrying out X-ray diffraction analysis on the residue after the reaction is completed to obtain other oxide components (Al)2O3-MgO-CaO-SiO2) After the chlorination product is further oxidized, the obtained oxidation product is analyzed by X-ray diffraction to be titanium dioxide (TiO)2) The analysis of the composition showed that the purity was 99.1%.
Example 3:
200.0g of iron ore concentrate (Fe) crushed into fine particles by a vibration mill are weighed2O3：47.3％，FeO：29.2％，TiO2: 12.4 percent of the total weight of the iron and titanium iron composite ore, 38.6g of graphite powder (with the carbon content of 99.9 percent) is added and then is placed in a planetary ball mill to be uniformly mixed, the powder after ball milling is placed in a high-temperature furnace after being pressed and formed, the temperature is slowly raised to 1700 ℃ in a semi-open system, the temperature is kept for 5 hours and then is cooled to the room temperature, and the X-ray diffraction analysis result of a reduction product shows that after the carbon-heat selective reduction, the iron oxide in the iron-titanium composite ore is reduced into metallic iron, and the titanium oxide is reduced into titaniumxNyOzAnd x/z is 0.5), the other components are not reduced. Crushing and grinding the upper block of the reduction product to below 200 meshes, performing chlorination treatment at 400 ℃, performing X-ray diffraction analysis on the residue after the reaction is completed, and displaying the result as other oxide components (Al)2O3-MgO-CaO-SiO2) After the chlorination product is further oxidized, the obtained oxidation product is analyzed by X-ray diffraction to be titanium dioxide (TiO)2) The analysis of the composition showed that the purity was 99.6%.
Comparative example 1 (reduction to Ti only)2O3)：
200.0g of ilmenite (FeO: 42.7%, TiO) crushed into fine particles by a vibration mill was weighed2: 47.5 percent), adding 21.4g of graphite powder (with the carbon content of 99.9 percent), placing the mixture in a planetary ball mill, uniformly mixing, placing the powder after ball milling in a high-temperature furnace after compression molding, controlling the atmosphere in the furnace to be argon, slowly heating to 2000 ℃, keeping the temperature for 3 hours, cooling to room temperature to obtain a reduction product divided into an upper part and a lower part, depositing the reduction product iron at the lower part,the upper part is analyzed by X-ray diffraction to obtain titanium sesquioxide (Ti) as shown in figure 62O3) And a non-reduced component. Crushing and grinding the upper block of the reduction product to below 200 meshes, performing chlorination treatment at 400 ℃, performing X-ray diffraction analysis on the residue after the reaction is completed, and obtaining the result shown in the attached figure 7 of the specification, wherein part of titanium sesquioxide (Ti) can be seen2O3) Is oxidized to titanium dioxide (TiO)2) This shows that if the titanium component in the ilmenite composite is not reduced to titanium (nitrogen) oxide (TiC)x(Ny)Oz) This will result in the chlorination reaction not proceeding normally.
Comparative example 2 (reduced to 0.33):
200.0g of ilmenite (FeO: 42.7%, TiO) crushed into fine particles by a vibration mill was weighed2: 47.5 percent of graphite powder (with the carbon content of 99.9 percent) which is 35.7g is added, the mixture is placed in a planetary ball mill and uniformly mixed, the powder after ball milling is placed in a high-temperature furnace after being pressed and formed, the temperature in the furnace is controlled to be argon atmosphere and is slowly raised to 2000 ℃, the temperature is kept for 3 hours and then is cooled to room temperature, a reduction product which is divided into an upper part and a lower part is obtained, iron which is the reduction product is deposited at the lower part, the structure of the upper part is analyzed through X-ray diffraction, as shown in the attached figure 8 of the specification0.25O0.75) And a non-reduced component. Crushing and grinding the upper block of the reduction product to below 200 meshes, performing chlorination treatment at 400 ℃, performing X-ray diffraction analysis on the residue after the reaction is completed, and obtaining the result shown in the attached figure 9 in the specification that the residual titanium monoxide (TiO) does not perform chlorination reaction, which shows that when the reduction product is titanium oxycarbide (TiC) (carbon (nitrogen) oxide)x(Ny)Oz) If the carbon-to-oxygen ratio of (2) is less than 0.5, the chlorination reaction will not proceed completely.
Comparative example 3 (reduced to C/O ═ 1.5):
200.0g of ilmenite (FeO: 42.7%, TiO) crushed into fine particles by a vibration mill was weighed2: 47.5 percent of graphite powder (with the carbon content of 99.9 percent) which is added with 45.7g of graphite powder, then the graphite powder is placed in a planetary ball mill to be mixed evenly, the powder is placed in a high temperature furnace after being pressed and formed after ball milling, and the furnace is controlledThe interior is nitrogen atmosphere, slowly heating to 2000 deg.C, heat-insulating for 3 hr, cooling to room temperature to obtain reduction product divided into upper and lower portions, the reduction product iron is deposited on the lower portion, and its upper portion is analyzed by X-ray diffraction and its structure is titanium oxycarbide (TiC)0.6O0.4) And a non-reduced component. Crushing and grinding the upper block of the reduction product to below 200 meshes, performing chlorination treatment at 400 ℃, performing X-ray diffraction analysis on the residue after the reaction is completed, and displaying the result as other oxide components (Al)2O3-MgO-CaO-SiO2) After the chlorination product is further oxidized, the obtained oxidation product is analyzed by X-ray diffraction to be titanium dioxide (TiO)2) The compositional analysis showed that the purity was 94.2%, indicating that titanium oxycarbide (TiC) when reducedx(Ny)Oz) When the carbon-oxygen ratio of (2) is more than 1, other oxides can be subjected to chlorination reaction at the same time, and the purity of the titanium tetrachloride product is further influenced.
Comparative example 4: reduction to TiC
200.0g of ilmenite (FeO: 42.7%, TiO) crushed into fine particles by a vibration mill was weighed2: 47.5 percent of graphite powder (with the carbon content of 99.9 percent) is added, 57.1g of graphite powder is placed in a planetary ball mill to be uniformly mixed, the powder is placed in a high-temperature furnace after being subjected to ball milling and is pressed and molded, the temperature in the furnace is controlled to be argon atmosphere and is slowly raised to 2000 ℃, the temperature is kept for 3 hours and then is cooled to room temperature, and the analysis result of X-ray diffraction on a reduction product shows that after the carbon-heat selective reduction, iron oxide in the ferrotitanium composite ore is reduced into metallic iron, titanium oxide is reduced into titanium carbide (TiC), and other components are not reduced. Crushing and grinding the upper block of the reduction product to below 200 meshes, performing chlorination treatment at 400 ℃, performing X-ray diffraction analysis on the residue after the reaction is completed, and displaying the result as other oxide components (Al)2O3-MgO-CaO-SiO2) After the chlorination product is further oxidized, the obtained oxidation product is analyzed by X-ray diffraction to be titanium dioxide (TiO)2) The compositional analysis showed that the purity was 91.1%, indicating that if the titanium component in the ilmenite composite was reduced to titanium carbide (TiC), this would result in the simultaneous evolution of other oxidesThe chlorination reaction occurs, which in turn affects the purity of the titanium tetrachloride product.
Claims (11)
1. A method for preparing a titanium product by taking a ferrotitanium composite ore as a raw material is characterized by comprising the following steps:
(1) carrying out crushing pretreatment on a ferrotitanium composite ore raw material;
(2) adding a carbon-containing reducing agent into the crushed and pretreated raw materials to obtain a mixture;
(3) heating the mixture under a certain atmosphere to carry out reduction reaction to obtain a reduction product containing titanium-rich phase substances, iron and slag phase components;
in the temperature rising process, the temperature is kept for a period of time after the set temperature is reached;
the set temperature is 1100-2200 ℃;
(4) discharging and separating iron in the reduction product to obtain a primary product containing a titanium-rich phase substance and a slag phase component;
(5) placing the primary product as a chlorination raw material in chlorination equipment, selectively chlorinating at a certain temperature, wherein in the selective chlorination process, slag phase components are kept in a solid state of oxides, the titanium-rich phase substance is chlorinated to generate titanium tetrachloride vapor, and condensing and collecting to obtain a titanium tetrachloride product with the purity higher than 99%;
the titanium-rich phase substance is titanium oxycarbide TiCmOnAnd titanium oxycarbonitride TiCxNyOzAt least one of:
the titanium oxycarbide TiCmOnWherein m + n =1 and 0.5. ltoreq. m/n. ltoreq.1;
TiC of titanium oxycarbonitridexNyOzWherein x + y + z =1, y is more than 0 and less than or equal to 1, and x/z is more than or equal to 0.5 and less than or equal to 1;
the temperatures at which the selective chlorination is carried out are: 200 ℃;
the amount of the carbonaceous reducing agent dosed in step (2) is such that all of the iron oxide in the ilmenite composite raw material can be reduced to metallic iron, and all of the titanium oxide in the ilmenite composite raw material can be reduced to the above-mentioned titanium oxycarbide, titanium oxycarbonitride or a mixture of both.
2. The method for preparing the titanium product by taking the ilmenite as the raw material according to claim 1, wherein the heat preservation period is 2-10 hours.
3. The method for preparing the titanium product by taking the ilmenite as the raw material according to claim 1, wherein the set temperature is 1100-1400 ℃.
4. The method for preparing a titanium product by using the ilmenite as the raw material according to claim 1, wherein the atmosphere in the step (3) comprises an argon, nitrogen or air atmosphere.
5. The method for preparing titanium products by taking the ilmenite as the raw material according to claim 1, characterized by further comprising the steps of ball-milling, uniformly mixing and press-forming the mixture after the step (2) and before the step (3).
6. The method for preparing titanium products by taking the ilmenite as the raw material according to claim 1, wherein the method for discharging and separating the iron in the reduction products in the step (4) comprises the following steps: directly discharging reduced molten iron at high temperature after the reduction reaction; or removing iron in the reduction product by adopting a solid iron gravity separation or magnetic separation mode.
7. The method for preparing titanium products by taking the ilmenite as the raw material according to claim 6, wherein when the mode of gravity separation or magnetic separation of solid iron is adopted, the method further comprises the step of pretreating the reduction product before discharging and separating iron, and the step of pretreating the reduction product comprises the dispersion treatment of crushing or ultrasonic or ball milling.
8. The method for preparing titanium products by using the ilmenite as the raw material according to claim 6, wherein when the magnetic separation of the solid iron is adopted, the reduction product is pretreated to obtain a magnetic separation raw material, and the magnetic separation raw material is placed in a magnetic separation device for magnetic separation.
9. A process according to any one of claims 1 to 8 for the production of a titanium product from an ilmenite composite ore, wherein the ilmenite composite ore comprises any one of ilmenite, vanadium titano-magnetite, ilmenite concentrate, iron ore concentrate, high titanium slag and rutile or a combination of any two or more thereof.
10. The method for preparing the titanium product by taking the titaniferous iron composite ore as the raw material according to any one of claims 1 to 8, wherein the carbonaceous reducing agent comprises any one or a combination of any two or more of activated carbon, graphite powder, charcoal, petroleum coke, asphalt, coke powder and coal powder.
11. A method for preparing titanium dioxide, which is characterized in that titanium tetrachloride prepared by any one of the methods in claims 1 to 10 is used as a raw material, and the titanium dioxide is prepared by oxidation treatment.
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| CN112320840A (en) * | 2020-11-04 | 2021-02-05 | 攀钢集团攀枝花钢铁研究院有限公司 | Boiling chlorination method for treating low-grade high-calcium magnesium titanium ore |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
| CN102505061A (en) * | 2012-01-04 | 2012-06-20 | 唐山奥特斯科技有限公司 | Method for preparing titanium-rich materials and granular irons by directly reducing titanic iron ore |
| CN102656287A (en) * | 2009-08-06 | 2012-09-05 | 齐诺卡有限公司 | Treatment of titanium ores |
| CN103695631A (en) * | 2013-12-19 | 2014-04-02 | 北京科技大学 | Mineral separation and enrichment process for ferrotitanium oxide ore |
| CN105907968A (en) * | 2016-05-05 | 2016-08-31 | 朱鸿民 | Method of extracting iron and titanium with ferrotitanium compound minerals as raw material and filtering equipment |
-
2018
- 2018-07-11 CN CN201810757820.3A patent/CN109055781B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
| CN102656287A (en) * | 2009-08-06 | 2012-09-05 | 齐诺卡有限公司 | Treatment of titanium ores |
| CN102505061A (en) * | 2012-01-04 | 2012-06-20 | 唐山奥特斯科技有限公司 | Method for preparing titanium-rich materials and granular irons by directly reducing titanic iron ore |
| CN103695631A (en) * | 2013-12-19 | 2014-04-02 | 北京科技大学 | Mineral separation and enrichment process for ferrotitanium oxide ore |
| CN105907968A (en) * | 2016-05-05 | 2016-08-31 | 朱鸿民 | Method of extracting iron and titanium with ferrotitanium compound minerals as raw material and filtering equipment |
Non-Patent Citations (1)
| Title |
|---|
| 碳氮氧化钛低温沸腾氯化法生产四氯化钛半工业试验;刘茂盛等;《四川冶金》;19841231(第02期);第61页右栏第2段至第65页左栏第1段 * |
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