CN109110804B - High-purity magneli phase titanium suboxide and preparation method thereof - Google Patents
High-purity magneli phase titanium suboxide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of inorganic materials, in particular to a preparation method of high-purity Magneli-phase titanium suboxide. The preparation method of the high-purity Magneli-phase titanium suboxide comprises the following steps: adding TiO into the mixture2Mixing the mixture with a binder, and granulating to obtain particles A with the diameter of 2-5 mm; alternately putting the particles A and the reducing agent into a reactor according to a layer of reducing agent and a layer of particles A, wherein the uppermost layer is the reducing agent; the particle A layers are all covered by single-layer particles A; except the uppermost reducing agent, the covering thickness of each layer of reducing agent is more than or equal to 2 cm; the covering thickness of the uppermost reducing agent is more than or equal to 10 cm; the particle size of the reducing agent is less than or equal to 74 mu m; reducing the reactor at 1250-1450 ℃ for 30-60 min, taking out the reactor after the reduction is finished, and cooling the reactor in an inert atmosphere to obtain a reduced product; and screening and cleaning the reduction product to obtain the high-purity Magneli-phase titanium suboxide. The prepared high-purity Magneli-phase titanium suboxide has high purity and low residual carbon content.
Description
Technical Field
The invention relates to the field of inorganic materials, in particular to high-purity Magneli-phase titanium suboxide and a preparation method thereof.
Background
In recent years, the application of magneli phase titanium suboxide in inert electrodes, fuel cells, lithium batteries, photocatalysis, conductive additives and other aspects has been reported, and the magneli phase titanium suboxide becomes one of the research hotspots of titanium functional materials at home and abroad. The magneli phase titanium oxide mainly has three preparation processes of a high-temperature reduction method, a laser ablation method and a sol-gel-sintering method. Preparation of the Magnesli-phase titanium oxide predominantly from TiO2As raw materials, the existing preparation method has the defects of long reaction process time, strict requirements on reaction atmosphere, difficulty in controlling the physicochemical properties of reaction products and the like.
The carbothermic method is widely applied to the field of material preparation due to the advantages of simple process, low cost, low requirement on equipment and the like.
Chinese patent No. 2017101201355 discloses a method for preparing a graphite-titanium suboxide composite material. The method is to mix graphite powder and titanium dioxide, and to cover the graphite powder on the surface of the mixed material uniformly, and to carry out high temperature reduction reaction. Although the method provides a means of reaction in the air atmosphere, the product prepared by the method is still a graphite-titanium suboxide composite material, the residual graphite or coal powder in the reduction product is difficult to effectively separate from the reduction product, high-purity Magneli-phase titanium suboxide cannot be prepared, and the expansion of the application field of the titanium suboxide is limited.
Therefore, it is necessary to explore and develop a new preparation process route for preparing high-purity Magneli-phase titanium suboxide by the carbothermic reduction method.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing high-purity Magneli-phase titanium suboxide by a carbothermic reduction method.
The preparation method of the high-purity Magneli-phase titanium suboxide comprises the following steps:
a. adding TiO into the mixture2Uniformly mixing the particles with a binder according to the weight ratio of 1: 0.05-0.1, granulating, and drying to obtain particles A with the diameter of 2-5 mm;
b. alternately putting the particles A and the reducing agent into a reactor according to a layer of reducing agent and a layer of particles A, wherein the uppermost covering layer is the reducing agent; wherein the reducing agent is graphite powder or coal powder; the particle A layers are all covered by single-layer particles A, and the covering thickness is the diameter of the particles A; except the uppermost reducing agent, the covering thickness of each layer of reducing agent is more than or equal to 2 cm; the covering thickness of the uppermost reducing agent is more than or equal to 10 cm; the particle size of the reducing agent is less than or equal to 74 mu m;
c. reducing the reactor at 1250-1450 ℃ for 30-60 min, taking out the reactor after the reduction is finished, and cooling the reactor in an inert atmosphere to obtain a reduced product;
d. screening the reduction product to obtain granular Magneli-phase titanium suboxide and a reducing agent;
f. and cleaning the residual reducing agent on the surface of the granular Malgneli-phase titanium suboxide to obtain the high-purity Malgneli-phase titanium suboxide.
Preferably, in step a, the binder is polyvinyl alcohol.
Preferably, in step a: the diameter of the particle A is 2.5-5 mm; more preferably, the particles A have a diameter of 2.5 mm.
Preferably, in step a: TiO 22The purity is more than 99%.
Preferably, in the step b, the covering thickness of each layer of reducing agent is 2.2-3 cm, and the covering thickness of the uppermost layer of reducing agent is 12-15 cm; preferably, each layer of reducing agent is covered to a thickness of 2.2cm, and the uppermost layer of reducing agent is covered to a thickness of 12 cm.
Preferably, in step b, the reactor is a graphite reactor.
Preferably, in step c, the inert atmosphere refers to argon or nitrogen.
Preferably, in step c, the reduction temperature is 1300 ℃ and the reduction time is 50 min.
Preferably, in step d, the screened reducing agent is returned to step b for continuous use in order to realize the recycling of the reducing agent and save the cost.
Preferably, in step f, ethanol can be used as the organic solvent for cleaning the residual reducing agent on the surface of the granular Magneli-phase titanium suboxide. The organic solvent is selected mainly in consideration of the cleaning effect on graphite, and any other organic solvent may be used as long as it can effectively clean graphite.
The invention also provides high-purity Malgneli-phase titanium suboxide which is prepared by the preparation method of the high-purity Malgneli-phase titanium suboxide. The purity of the high-purity Magneli-phase titanium suboxide prepared by the method is more than or equal to 99%, and the content of C in the product is less than or equal to 0.46%.
The invention has the beneficial effects that:
1. the high-purity Magneli-phase titanium suboxide is prepared in the air atmosphere, vacuum or protective gas is not needed, and the requirements on production equipment and production environment are low.
2. The process can prepare high-purity Magneli-phase titanium suboxide within a short reduction time (30-60 min).
3. The method has simple process, low raw material price and huge raw material reserves, and is convenient for large-scale industrial production.
4. The high-purity Magneli-phase titanium suboxide prepared by the method has high purity and low residual carbon content.
Drawings
FIG. 1 XRD pattern of a product prepared according to example 1 of the present invention;
FIG. 2 XRD pattern of the product prepared in example 2 of the present invention;
FIG. 3 XRD pattern of the product prepared in example 3 of the present invention;
Detailed Description
The invention aims to solve the technical problem of providing a method for preparing high-purity Magneli-phase titanium suboxide by a carbothermic reduction method. The core of the invention is to adopt a granulation method, and utilize the particle size difference between graphite powder (reducing agent) and titanium dioxide particles to realize the preparation of high-purity Magneli-phase titanium suboxide by adopting a carbothermic reduction process, thereby overcoming the technical problem that the residual carbon of the traditional carbothermic reduction product is difficult to remove to obtain a high-purity product.
The preparation method of the high-purity Magneli-phase titanium suboxide comprises the following steps:
a. adding TiO into the mixture2Uniformly mixing the particles with a binder according to the weight ratio of 1: 0.05-0.1, granulating, and drying to obtain particles A with the diameter of 2-5 mm;
b. alternately putting the particles A and the reducing agent into a reactor according to a layer of reducing agent and a layer of particles A, wherein the uppermost covering layer is the reducing agent; wherein the reducing agent is graphite powder or coal powder; the particle A layers are all covered by single-layer particles A, and the covering thickness is the diameter of the particles A; except the uppermost reducing agent, the covering thickness of each layer of reducing agent is more than or equal to 2 cm; the covering thickness of the uppermost reducing agent is more than or equal to 10 cm; the particle size of the reducing agent is less than or equal to 74 mu m;
c. reducing the reactor at 1250-1450 ℃ for 30-60 min, taking out the reactor after the reduction is finished, and cooling the reactor in an inert atmosphere to obtain a reduced product;
d. screening the reduction product to obtain granular Magneli-phase titanium suboxide and a reducing agent;
f. and cleaning the residual reducing agent on the surface of the granular Malneli-phase titanium suboxide to obtain the granular Malneli-phase titanium suboxide with high purity.
The invention needs to firstly prepare TiO2The reason for granulation is to generate a particle size difference between the titanium dioxide and the graphite powder (reducing agent), so that the reduction product can be effectively separated from the unreacted graphite powder by adopting a screening mode after reduction. In addition, the diameter of the particle A needs to be limited within the range of 2-5 mm, and the purity of the prepared titanium monoxide can be influenced when the diameter is too large or too small. The larger the diameter of the particle A is, the adverse effect is caused on the transmission of CO gas into the particle, so that the reaction is insufficient in a certain reduction time, and partial TiO is generated2Not reduced, thereby affecting the purity of the reduced product; when the diameter of the particles A is too small (< 2mm), the separation of the product, Maleli phase, titanium suboxide from the graphite powder is affected, resulting in the production of Maleli phase titanium suboxide of insufficient purity.
The invention adopts two materials which are layered and staggered to stack in order to enlarge the graphite powder and TiO2The contact area of the particles improves the kinetics of the reduction process and shortens the reduction time.
The reducing agent adopted by the invention has the granularity of less than or equal to 74 mu m, the smaller the granularity of the reducing agent is, the higher the activity is in a high-temperature state, and the reducing agent is beneficial to forming and maintaining the reducing atmosphere of the whole reaction system and the reaction. And the titanium dioxide and the reducing agent can generate particle size difference, so that a reduction product can be effectively separated from unreacted graphite powder in a screening mode after reduction.
Preferably, in step a, the binder is polyvinyl alcohol, and the polyvinyl alcohol can be decomposed into H in a high-temperature process2O and CO2And the purity of the product is not influenced.
In order to increase the purity of the titanium suboxide produced, preferably, TiO2And the binder in a weight ratio of 1: 0.05.
In order to improve the degree of converting titanium dioxide into titanium suboxide and the purity of the titanium suboxide, preferably, in the step a, the diameter of the particles A is 2.5-5 mm; more preferably, the particles A have a diameter of 2.5 mm.
To liftIncreasing the degree of conversion of titanium dioxide to titanium suboxide and increasing the purity of titanium suboxide, preferably, in step a, the TiO is2The purity is more than 99%.
In order to improve the degree of converting titanium dioxide into titanium suboxide and the purity of the prepared product magneli phase titanium suboxide, preferably, in the step b, the covering thickness of each layer of reducing agent is 2.2-3 cm, and the covering thickness of the uppermost layer of reducing agent is 12-15 cm; when the covering thickness of each layer of reducing agent is 2.2cm, and the covering thickness of the uppermost reducing agent is 12cm, the C content in the prepared product is the lowest.
Preferably, in step b, the reactor is a graphite reactor.
Preferably, in step c, the inert atmosphere refers to argon or nitrogen.
In order to increase the degree of conversion of titanium dioxide into titanium monoxide and the purity of titanium monoxide, it is preferable that the reduction temperature in step c is 1300 ℃ and the reduction time is 50 min.
Preferably, in step d, the screened reducing agent is returned to step b for continuous use in order to realize the recycling of the reducing agent and save the cost.
Preferably, in step f, ethanol can be used as the organic solvent for cleaning the residual reducing agent on the surface of the granular Magneli-phase titanium suboxide. The organic solvent is selected mainly in consideration of the cleaning effect on graphite, and any other organic solvent may be used as long as it can effectively clean graphite.
The invention also provides high-purity Malgneli-phase titanium suboxide which is prepared by the preparation method of the high-purity Malgneli-phase titanium suboxide. The purity of the high-purity Magneli-phase titanium suboxide prepared by the method is more than or equal to 99 percent, and the graphite content is less than or equal to 0.46 percent.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
In the following examples, the particle size of the graphite powder used was not more than 74 μm; the binder is polyvinyl alcohol.
Example 1
Taking 100g of TiO25g of binder, granulating after uniformly mixing and drying to obtain granules A, wherein the diameter of the granules A is 2.5 mm; then, the particles A and the graphite powder are alternately arranged in a graphite crucible according to a layer of graphite powder and a layer of particles A, and the covering layer at the uppermost layer is a graphite powder layer; wherein, except the uppermost graphite powder layer, the covering thickness of each layer of graphite powder is 2.2cm, the covering thickness of the uppermost graphite powder layer is 12cm, the covering layer of the particle A is a single-layer particle A, and the covering thickness is 2.5mm of the diameter of the particle A; and then placing the graphite crucible into a high-temperature furnace, reducing at 1300 ℃ for 50min in the air atmosphere, taking out the crucible quickly after the reduction time is reached, introducing argon gas for protection, cooling to room temperature, screening the reduced product to obtain granular Magneli-phase titanium suboxide, and cleaning and finely grinding the granular Magneli-phase titanium suboxide by using absolute ethyl alcohol to obtain a high-purity Magneli-phase titanium suboxide product. The XRD pattern of the product is shown in FIG. 1, which proves that the phase composition of the product is titanium suboxide. The product was tested and the residual carbon content of the product of this example was 0.17%.
Example 2
Taking 100g of TiO210g of binder, uniformly mixing, granulating and drying to obtain particles A, wherein the diameter of the particles A is 2mm, and then placing the particles A and graphite powder into a graphite crucible in a staggered manner according to a layer of graphite powder and a layer of particles A, wherein the uppermost covering layer is a graphite powder layer; wherein, except the graphite powder layer at the uppermost layer, the covering thickness of each layer of graphite powder is 2.5cm, the covering thickness of the graphite powder layer at the uppermost layer is 12cm, the covering layer of the particle A is a single-layer particle A, and the covering thickness is 2 mm; and then placing the graphite crucible into a high-temperature furnace, reducing the graphite crucible at 1350 ℃ in an air atmosphere for 40min, taking out the graphite crucible quickly after the reduction time is reached, introducing argon gas for protection, cooling to room temperature, screening the reduced product to obtain granular Magneli-phase titanium suboxide, and cleaning and finely grinding the granular Magneli-phase titanium suboxide by using absolute ethyl alcohol to obtain a high-purity Magneli-phase titanium suboxide product. The XRD pattern of the product is shown in FIG. 2, which demonstrates that the phase composition is titanium suboxide. For productsThe test was conducted and the product of this example had a residual carbon content of 0.46%.
Example 3
Taking 100g of TiO210g of binder, uniformly mixing, granulating and drying to obtain particles A, wherein the diameter of the particles A is 5mm, and then placing the particles A and graphite powder into a graphite crucible in a staggered manner according to a layer of graphite powder and a layer of particles A, wherein the uppermost covering layer is a graphite powder layer; wherein, except the uppermost graphite powder layer, the covering thickness of each layer of graphite powder is 3cm, the covering thickness of the uppermost graphite powder layer is 15cm, the covering layer of the particle A is a single-layer particle A, and the covering thickness is 5 mm; and then placing the graphite crucible into a high-temperature furnace, reducing at 1400 ℃ for 30min in the air atmosphere, taking out the crucible quickly after the reduction time is reached, introducing argon for protection, cooling to room temperature, screening the reduced product to obtain granular Magneli-phase titanium suboxide, and cleaning and finely grinding the granular Magneli-phase titanium suboxide by using absolute ethyl alcohol to obtain a high-purity Magneli-phase titanium suboxide product. The XRD pattern of the product is shown in FIG. 3, which demonstrates that the phase composition is titanium suboxide. The product was tested and the residual carbon content of the product of this example was 0.27%.
Claims (11)
1. The preparation method of the high-purity Magneli-phase titanium suboxide is characterized by comprising the following steps of:
a. adding TiO into the mixture2Uniformly mixing the particles with a binder according to the weight ratio of 1: 0.05-0.1, granulating, and drying to obtain particles A with the diameter of 2-5 mm; wherein the binder is polyvinyl alcohol;
b. alternately putting the particles A and the reducing agent into a reactor according to a layer of reducing agent and a layer of particles A, wherein the uppermost covering layer is the reducing agent; wherein the reducing agent is graphite powder or coal powder; the particle A layers are all covered by single-layer particles A, and the covering thickness is the diameter of the particles A; except the uppermost reducing agent, the covering thickness of each layer of reducing agent is more than or equal to 2 cm; the covering thickness of the uppermost reducing agent is more than or equal to 10 cm; the particle size of the reducing agent is less than or equal to 74 mu m;
c. reducing the reactor at 1250-1450 ℃ for 30-60 min, taking out the reactor after the reduction is finished, and cooling the reactor in an inert atmosphere to obtain a reduced product;
d. screening the reduction product to obtain granular Magneli-phase titanium suboxide and a reducing agent;
f. and cleaning the residual reducing agent on the surface of the granular Malgneli-phase titanium suboxide to obtain the high-purity Malgneli-phase titanium suboxide.
2. The method for preparing high-purity magneli-phase titanium suboxide according to claim 1, wherein in step a: the diameter of the particles A is 2.5-5 mm.
3. The method for preparing high-purity magneli-phase titanium suboxide according to claim 2, wherein in step a: the diameter of the granules A was 2.5 mm.
4. The process for the preparation of high purity magneli-phase titanium suboxide according to claim 1 or 2, characterized in that in step a: TiO 22The purity is more than 99%.
5. The method for preparing high-purity Magnesli-phase titanium suboxide according to claim 1 or 2, wherein in the step b, the coverage thickness of each layer of reducing agent is 2.2-3 cm, and the coverage thickness of the uppermost layer of reducing agent is 12-15 cm.
6. The method according to claim 5, wherein in step b, the covering thickness of each layer of reducing agent is 2.2cm, and the covering thickness of the uppermost layer of reducing agent is 12 cm.
7. The process for the preparation of high purity magneli-phase titanium suboxide according to claim 1 or 2, characterized in that: in the step b, the reactor is a graphite reactor.
8. The process for the preparation of high purity magneli-phase titanium suboxide according to claim 1 or 2, characterized in that: in step c, the inert atmosphere refers to argon or nitrogen.
9. The process for the preparation of high purity magneli-phase titanium suboxide according to claim 1 or 2, characterized in that: in the step c, the reduction temperature is 1300 ℃, and the reduction time is 50 min.
10. The method for preparing high-purity magneli-phase titanium suboxide according to claim 1, wherein in the step d, the screened reducing agent is returned to the step b for further use.
11. The high-purity Malgneli-phase titanium suboxide is characterized by being prepared by the preparation method of the high-purity Malgneli-phase titanium suboxide as claimed in any one of claims 1 to 10.
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