CN1693209A - Process for preparing titanic schorl titanium dioxide by adding powder reducing agent mode - Google Patents
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Abstract
A method for preparing titanic schorl titanium dioxide by adding powder reducing agent mode, the preparing steps is: (1) adding the power into the material which is composed of metatitanic acid or anatase titanium dioxide, and mixing uniform, the power reducing agent is one of the carbon power, zinc power, aluminum power, magnesium power, iron power. The total amount of the power reducing agent is the 0.5%~6% of the TiO[2] net weight in material. (2) to calcine the material made by step one among the temperature of 820 ~ 910 DEG C, then cooling until normal temperature after 0.5~5 hours heat preservation, thus the rutile tirania will be obtained. This method avoids the disadvantage that grains vary large as well as particle size distributes widely caused by long transformation time of the crystal form which is made by the traditional crystal seed calcination method of preparing titanic schorl titanium dioxide from metatitanic acid, and also this method reduces the crystal sedd calcination process and calcination time, thus can save internal friction and shorten production cycle, and improve output and decrease cost.
Description
Technical Field
The invention belongs to the field of chemical engineering and preparation of inorganic non-metallic materials, and particularly relates to a method for preparing rutile titanium dioxide by adding a powdery reducing agent to reduce tetravalent titanium atoms in metatitanic acid or anatase titanium dioxide into trivalent titanium atoms and carrying out high-temperature calcination.
Background
Titanium oxide TiO2Titanium dioxide is commonly called as a basic material in chemical industry and electronic industry, and titanium dioxide has three crystal forms: the brookite type, the anatase type and the rutile type have application values of only the anatase type and the rutile type. In the fields of pigments and electronic materials, rutile titanium dioxide has higher application value than anatase titanium dioxide, but the preparation process is relatively complex.
At present, the production process of rutile titanium dioxide at home and abroad mainly comprises two major types: namely a seed crystal calcination method and a chlorination method of metatitanic acid which is a hydrolysate of a sulfuric acid method. In few European and American countries, the production of rutile titanium dioxide is mainly carried out by a chlorination process, and in China, except for the chlorination process in the Jinzhou titanium dioxide factory, the other processes are sulfuric acid process processes. The technology for producing rutile type titanium dioxide by chlorination process is monopolized by a few foreign companies. Due to the limitation of technical conditions, most manufacturers in China currently adopt a seed crystal calcination method of metatitanic acid which is a hydrolysate of a sulfuric acid method to produce rutile titanium dioxide.
Chinese patent application No. 94111732.4 discloses a method for preparing rutile titanium dioxide, which is to inject ammonia gas into a certain proportion of titanium tetrachloride and alcohol solvent to prepare titanium dioxide. This method for producing titanium dioxide from titanium tetrachloride as a main raw material has a problem of high production cost.
The Chinese patent application No. 01118739.5 discloses a method for preparing rutile titanium dioxide by using titanate as a raw material, and the method has higher raw material price and is only suitable for laboratory preparation but not suitable for industrial production.
Chinese patent application No. 02146104.X discloses a method for preparing double-effect crystal seeds (the crystal seeds contain SnO)2、ZnO2Etc.) at a relatively low temperature. The method belongs to a seed crystal method in a rutile type titanium dioxide preparation method.
The Chinese patent application No. 98113128.X discloses a method for preparing rutile titanium dioxide by adding metatitanic acid autohydrolysis seed crystal to treat ilmenite in the presence of dilute hydrochloric acid. The method only changes the rutile type titanium dioxide prepared by the traditional crystal seed calcining method in some crystal seed treatment, and still has the problems of longer crystal form conversion process, increased average particle size, widened particle size distribution, poor batch sample reproducibility and the like inherent in the traditional crystal seed calcining method.
In conclusion, there is a need to develop a new method for preparing rutile titanium dioxide, which is more convenient than the existing seed crystal method, is different from the existing seed crystal method, is suitable for industrial production, improves the product quality, enlarges the production scale, reduces the cost and eliminates the environmental pollution.
Disclosure of Invention
The invention aims to provide a novel method for preparing rutile titanium dioxide, namely, metatitanic acid or anatase titanium dioxide is used as a main raw material, a powdery reducing agent is added to partially reduce tetravalent titanium atoms into trivalent titanium atoms, lattice distortion is caused by partial valence change of the titanium atoms at high temperature, and crystal form conversion is realized in a short time to prepare the rutile titanium dioxide.
The preparation method is characterized by comprising the following steps:
(1) adding a powdery reducing agent into a raw material consisting of metatitanic acid or anatase titanium dioxide, and uniformly mixing, wherein the powdery reducing agent is at least one of carbon powder, zinc powder, aluminum powder, magnesium powder and iron powder, and the total amount of the added powdery reducing agent is TiO in the raw material20.5 to 6 percent of net weight;
(2) and (2) heating the material prepared in the step (1) to 820-910 ℃ for calcining, preserving heat for 0.5-5 hours, and naturally cooling to normal temperature to obtain the rutile titanium dioxide.
In the step (1) of the present invention, the particle size of the powdery reducing agent is not required. The powdery reducing agent is at least one of carbon powder, zinc powder, aluminum powder, magnesium powder and iron powder, namely, the powdery reducing agent can be one of the carbon powder, the zinc powder, the aluminum powder, the magnesium powder and the iron powder, and can also be a mixture formed by randomly combining the components. For example, when the powdery reducing agent is a mixture of two components, it may be a mixture of carbon and zinc powder, a mixture of carbon and aluminum powder, a mixture of carbon and magnesium powder, a mixture of carbon and iron powder, a mixture of zinc and aluminum powder, a mixture of zinc and magnesium powder, a mixture of zinc and iron powder, a mixture of aluminum and magnesium powder, and a mixture of magnesium and iron powder. By analogy, when the powdery reducing agent is a mixture formed by combining three or four or five components, the powdery reducing agent can be a mixture of carbon, zinc and aluminum powder, a mixture of zinc, aluminum and magnesium powder, a mixture of aluminum, magnesium and iron powder, a mixture of carbon, zinc, aluminum and magnesium powder, a mixture of zinc, aluminum, magnesium and iron powder, a mixture of carbon, zinc, aluminum, magnesium and iron powder and the like.
When the powdery reducing agent is the above-mentioned mixture, the weight ratio of the components in the mixture is not required either, so long as the total weight (sum of the net weights) of the mixture is TiO in the raw material20.5 to 6 percent of net weight.
In the step (1), when anatase titanium dioxide is used as a raw material, no chemical reaction occurs in the process of adding a powdery reducing agent to the raw material and uniformly mixing. When metatitanic acid is used as a raw material and the powdery reducing agent is only carbon powder, a chemical reaction does not occur.
In the step (1), when metatitanic acid is used as a raw material and the powdery reducing agent at least comprises one of zinc powder, aluminum powder, magnesium powder and iron powder, the zinc powder or the aluminum powder or the magnesium powder or the iron powder in the powdery reducing agent undergoes a partial redox reaction with metatitanic acid during mixing, and the partial redox reaction reduces a part of tetravalent titanium ions in metatitanic acid to trivalent titanium ions.
In this step, when the added powdery reducing agent contains zinc powder, the main chemical reaction equation is as follows:
when the added powdery reducing agent contains aluminum powder, the main chemical reaction equation is as follows:
when the added powdery reducing agent contains magnesium powder, the main chemical reaction equation is as follows:
when the added powdery reducing agent contains iron powder, the main chemical reaction equation is as follows:
in the method of the present invention, when metatitanic acid is used as a raw material and the powdery reducing agent at least comprises one of zinc powder, aluminum powder, magnesium powder and iron powder, if the prepared rutile type titanium dioxide finished product is used in a field with low quality requirement, that is, impurities remained after the reaction of the powdery reducing agent are allowed to remain in the finished product, the step (2) can be performed after the operations of adding the powdery reducing agent and uniformly mixing in the step (1) are completed. In the step (2), the powder-like reducing agent zinc powder or aluminum powder or magnesium powder or iron powder which is not completely reacted continues to perform partial oxidation-reduction reaction with metatitanic acid in the heating process, and the oxidation-reduction reaction reduces partial tetravalent titanium ions in metatitanic acid to trivalent titanium ions. The main equations are still in the form of equations (1) (2) (3) and (4).
However, when metatitanic acid is used as a raw material and the powdery reducing agent contains at least one of zinc powder, aluminum powder, magnesium powder, and iron powder, if the desired product is high-quality rutile titanium dioxide used in the field of electronic materials and the like, the residual ions after the reaction of the added powdery reducing agent should be removed while maintaining a part of the titanium element in a trivalent ion state after the completion of the above-mentioned operation of adding and uniformly mixing the powdery reducing agent in step (1). The specific method comprises the following steps: after the powdery reducing agent is added and uniformly mixed, adding hydrochloric acid into the obtained material, adjusting the acidity to ensure that the PH value of the material is less than or equal to 2.0, and reacting metatitanic acid with the powdery reducing agent until the powdery reducing agent completely disappears, so that the oxidation-reduction reaction is not continued in the step (2); and then, adjusting the pH value of the material to 2.0-4.0 by using ammonia water, washing the material by using purified water, carrying out chemical analysis on the material in the washing process, and stopping washing when the mass percentage of the residual powdery reducing agent ions and the weight percentage of chloride ions introduced by hydrochloric acid are less than or equal to 0.003%, wherein impurities in the material can be considered to be completely washed. After the above-mentioned acidity adjustment and water washing operations are completed, the process proceeds to step (2).
In the step (2), when metatitanic acid is used as a raw material and the powdered reducing agent is carbon powder, an oxidation-reduction reaction occurs during heating to reduce part of tetravalent titanium ions in metatitanic acid to trivalent titanium ions, and the main chemical reaction equation is as follows:
in the step (2), when anatase titanium dioxide is used as a raw material, the added powdered reducing agent such as carbon powder or zinc powder or aluminum powder or magnesium powder or iron powder and the like performs partial redox reaction with the anatase titanium dioxide in the heating process, and the redox reaction reduces partial tetravalent titanium atoms in the titanium dioxide to trivalent titanium atoms.
In this step, when anatase titanium dioxide is used as the raw material and the powdered reducing agent is carbon powder, the main chemical reaction equation is as follows:
when anatase titanium dioxide is used as a raw material and the added powdery reducing agent is zinc powder, the main chemical reaction equation is as follows:
when anatase titanium dioxide is used as a raw material and the added powdery reducing agent is aluminum powder, the main chemical reaction equation is as follows:
when anatase titanium dioxide is used as a raw material and the added powdery reducing agent is magnesium powder, the main chemical reaction equation is as follows:
when anatase titanium dioxide is used as a raw material and the added powdery reducing agent is iron powder, the main chemical reaction equation is as follows:
in the above step (2), whether the main raw material is metatitanic acid or anatase titanium dioxide, trivalent titanium oxide titanium sesquioxide Ti is produced by partial reduction during calcination2O3During the calcination, this small amount of titanium sesquioxide Ti formed as a result of the partial reduction2O3The crystal lattice which tends to develop towards the generation of anatase titanium dioxide originally generates crystal lattice distortion at 680-780 ℃ and forms rutile titanium dioxide crystal form at the temperature above 820 ℃, and in the process, titanium sesquioxide Ti2O3Titanium dioxide is also oxidized in air and is in the rutile crystal form. Very important is that: the lattice distortion can be completed in a short time, thereby ensuring the excellent properties of small powder particle size and uniform particle size distribution.
In the step (2), before the material is heated to 820-910 ℃ for calcination, the material may be dried and ground (but the material may be directly calcined without drying and grinding). Generally, the drying and grinding of the material are beneficial to complete the reaction of the material during the calcination process and to improve the quality of the product, so the invention recommends to operate in this way. In specific implementation, the materials can be dried at the temperature of 100-420 ℃, and then ground to enable the particle size of the materials to be less than 1 micron.
In the step (2) of the present invention, the time taken to heat to 820-910 ℃ does not affect the reaction result, and is not required, for example, the heating process can be 30 minutes or 5 hours, but generally can be controlled to 0.5-5 hours.
In the step (2), the main chemical reaction equation of titanium dioxide generated by calcining metatitanic acid is as follows:
it should be noted that: when carbon powder is selected as the powdery reducing agent, the residual amount after the reaction is volatilized in the form of carbon dioxide at high temperature, so that special removal is not needed, and the main chemical equation is as follows:
the following are the results of the test analysis of the product made by the method of the invention:
x-ray diffraction analysis: the obtained powder is rutile titanium dioxide, and the rutile crystal form content in the titanium dioxide is more than 99.5 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
The inventive contribution of the invention lies in that a third method for producing titanium dioxide except a chlorination method and a sulfuric acid seed crystal calcining method is established from the mechanism: the method is characterized in that a tetravalent titanium atom is partially changed into a trivalent titanium atom by adding a powdery reducing agent, so that the crystal lattice of titanium dioxide is distorted, and finally, a rutile type titanium dioxide crystal form is formed at the temperature of 820-910 ℃.
The preparation method of the rutile titanium dioxide has the following positive effects: (1) the production of the process can be realized on the existing sulfuric acid method titanium dioxide production line by adding the powdery reducing agent and canceling the seed crystal calcining process; (2) the defects that crystal grains are easy to grow and the particle size distribution range is wide due to long crystal form conversion time of a traditional crystal seed calcining method for preparing rutile titanium dioxide by metatitanic acid are overcome, so that the crystal form conversion is completed in a short time, the crystal form conversion time can be comparable to that of a titanium tetrachloride gas phase oxidation method, and the characteristics of fine powder particle size and concentrated and uniform particle size distribution are ensured; (3) and because the seed crystal calcining process is reduced, the calcining time is reduced, the internal consumption can be saved, the production period can be shortened, the yield can be improved, and the cost can be reduced.
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples.
Drawings
FIG. 1 is an X-ray diffraction chart of the titanium dioxide powder produced in example 1.
FIG. 2 is a scanning electron micrograph of the titanium dioxide powder produced in example 1.
Detailed Description
Example 1: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) corresponding to the pure TiO content2100 kg of metatitanic acid is taken as a raw material, 0.5 kg of carbon powder is added as a powdery reducing agent, and the mixture is stirred for 1.5 hours to be uniformly mixed; (2) drying at about 100 deg.C, grinding to make particle size of material less than 1 micrometer, heating to 820 deg.C, calcining, holding at the above temperature for 5 hr to obtain loose agglomerated powder, and slightly grinding to obtain rutile type IITitanium oxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.5%. The X-ray diffraction pattern of the obtained titanium dioxide powder is shown in FIG. 1.
Scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns. The scanning electron micrograph of the prepared titanium dioxide powder is shown in figure 2.
Example 2: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) corresponding to the pure TiO content2100 kg of metatitanic acid is taken as a raw material, 2 kg of zinc powder is added as a powdery reducing agent, and the mixture is stirred for 1.5 hours to be uniformly mixed; (2) drying and grinding at about 150 ℃, heating to 840 ℃ for calcining, keeping the temperature within the temperature range for 4.5 hours to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 3: the rutile titanium dioxide preparation method in the embodiment is similar to that in embodiment 2, except that in step (1) of the embodiment, after the powdery reducing agent is added and uniformly mixed, hydrochloric acid is added into the obtained material, the acidity is adjusted to enable the pH of the material to be less than or equal to 2.0, metatitanic acid and the powdery reducing agent are reacted until the powdery reducing agent completely disappears, then ammonia water is used for adjusting the pH of the material to be 2.0-4.0, purified water is used for washing the material, chemical analysis is carried out on the material in the washing process, after the material is washed for 7 times by using deionized water with the volume being 3 times that of the material, a detection result shows that the residual mass percentage content of the powdery reducing agent ions and the weight percentage content of chloride ions introduced by the hydrochloric acid are less than 0.003%, then the washing is stopped, and the step (2) is carried out.
The product obtained in this example is high-quality rutile titanium dioxide used in the fields of electronic materials and the like.
Example 4: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) corresponding to the pure TiO content2100 kg of metatitanic acid is taken as a raw material, 1 kg of aluminum powder is added as a powdery reducing agent, and the mixture is stirred for 1.5 hours to be uniformly mixed; (2) drying at about 20 ℃ and grinding, heating to 850 ℃ for calcination, and keeping the temperature within the temperature range for 4 hours to obtain loose lumpsAnd grinding the aggregated powder to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 5: the rutile titanium dioxide preparation method in the embodiment is similar to embodiment 4, except that in step (1) of the embodiment, after the powdery reducing agent is added and uniformly mixed, hydrochloric acid is added into the obtained material, the acidity is adjusted to enable the pH of the material to be less than or equal to 2.0, metatitanic acid and the powdery reducing agent are reacted until the powdery reducing agent completely disappears, then ammonia water is used for adjusting the pH of the material to be 2.0-4.0, purified water is used for washing the material, chemical analysis is carried out on the material in the washing process, after the material is washed for 7 times by using deionized water with the volume being 3 times of the volume of the material, a detection result shows that the residual mass percentage content of the powdery reducing agent ions and the weight percentage content of chloride ions introduced by the hydrochloric acid are less than 0.003%, then the washing is stopped, and the step (2) is carried out.
The product obtained in this example is high-quality rutile titanium dioxide used in the fields of electronic materials and the like.
Example 6: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) corresponding to the pure TiO content2100 kg of metatitanic acid is taken as a raw material, 2.5 kg of magnesium powder is added as a powdery reducing agent, and the mixture is stirred for 1.5 hours to be uniformly mixed; (2) drying and grinding at about 220 ℃, heating to 860 ℃ for calcining and preserving heat for 3.5 hours to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 7: the rutile titanium dioxide preparation method in the embodiment is similar to that in embodiment 6, except that in step (1) of the embodiment, after the powdery reducing agent is added and uniformly mixed, hydrochloric acid is added into the obtained material, the acidity is adjusted to enable the pH of the material to be less than or equal to 2.0, metatitanic acid and the powdery reducing agent are reacted until the powdery reducing agent completely disappears, then ammonia water is used for adjusting the pH of the material to be 2.0-4.0, purified water is used for washing the material, chemical analysis is carried out on the material in the washing process, after the material is washed for 7 times by using deionized water with the volume being 3 times that of the material, a detection result shows that the residual mass percentage content of the powdery reducing agent ions and the weight percentage content of chloride ions introduced by the hydrochloric acid are less than 0.003%, then the washing is stopped, and the step (2) is carried out.
The product obtained in this example is high-quality rutile titanium dioxide used in the fields of electronic materials and the like.
Example 8: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) corresponding to the pure TiO content2100 kg of metatitanic acid is taken as a raw material, 3 kg of iron powder is added as a powdery reducing agent, and the mixture is stirred for 1.5 hours to be uniformly mixed; (2) drying and grinding at about 310 ℃, heating to 870 ℃, calcining and preserving heat for 3 hours to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 9: the rutile titanium dioxide preparation method in the embodiment is similar to that in embodiment 8, except that in step (1) of the embodiment, after the powdery reducing agent is added and uniformly mixed, hydrochloric acidis added into the obtained material, the acidity is adjusted to enable the pH of the material to be less than or equal to 2.0, metatitanic acid and the powdery reducing agent are reacted until the powdery reducing agent completely disappears, then ammonia water is used for adjusting the pH of the material to be 2.0-4.0, purified water is used for washing the material, chemical analysis is carried out on the material in the washing process, after the material is washed for 7 times by using deionized water with the volume being 3 times that of the material, a detection result shows that the residual mass percentage content of the powdery reducing agent ions and the weight percentage content of chloride ions introduced by the hydrochloric acid are less than 0.003%, then the washing is stopped, and the step (2) is carried out.
The product obtained in this example is high-quality rutile titanium dioxide used in the fields of electronic materials and the like.
Example 10: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) taking anatase type TiO2100 kg of the raw material is added with 3.5 kg of carbon powder as a powdery reducing agent and stirred for 1.5 hours to be uniformly mixed; (2) drying and grinding at about 320 ℃, heating to 880 ℃, calcining and preserving heat for 2.5 hours to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 11: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) taking anatase type TiO2100 kg of the raw material is added with 4 kg of zinc powder as a powdery reducing agent and stirred for 1.5 hours to be uniformly mixed; (2) drying and grinding at about 330 ℃, heating to 890 ℃, calcining and preserving heat for 2 hours to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 12: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) taking anatase type TiO2100 kg of raw material is added with 4.5 kg of aluminum powder as powdery reducing agent and stirred for 1.5 hours to be uniformly mixed; (2) drying at 350 deg.C, grinding, heating to 90 deg.CCalcining at 0 ℃ and keeping the temperature for 1.5 hours to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanningelectron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 13: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) taking anatase type TiO2100 kg of magnesium powder is used as a raw material, 5 kg of magnesium powder is used as a powdery reducing agent, and the mixture is stirred for 1.5 hours to be uniformly mixed; (2) drying and grinding at about 380 ℃, heating to 910 ℃ for calcining, keeping the temperature within the temperature range for 1 hour to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: the obtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 14: the preparation method of the rutile titanium dioxide in the embodiment is carried out according to the following steps:
(1) taking anatase type TiO2100 kg of raw materials are added with 6 kg of iron powder as a powdery reducing agent and stirred for 1.5 hours to be uniformly mixed; (2) drying and grinding at about 420 ℃, heating to 910 ℃, calcining and keeping the temperature for 0.5 hour to obtain loose agglomerated powder, and slightly grinding to obtain rutile type titanium dioxide powder.
The following is a test analysis of the product made by the method of this example:
x-ray diffraction analysis: theobtained powder is rutile type titanium dioxide, and the rutile crystal form content in the titanium dioxide is 99.0 percent;
scanning electron microscope analysis: 90% of the particle size distribution is in the range of 0.18 to 0.27 microns.
Example 15: the rutile titanium dioxide was prepared in a similar manner to example 1, except that in this example, 0.4 kg of carbon powder and 0.2 kg of zinc powder were mixed to form the powdery reducing agent, and the total amount of the powdery reducing agent added was 0.6 kg.
Example 16: the rutile type titanium dioxide was prepared in a similar manner to example 2, except that in this example, 2 kg of a powdery reducing agent and 0.5 kg of an aluminum powder were mixed together to form a mixture, and the total amount of the powdery reducing agent added was 2.5 kg.
Example 17: the rutile type titanium dioxide was prepared in a similar manner to example 4, except that in this example, 1 kg of aluminum powder and 0.2 kg of magnesium powder were mixed together as a powdery reducing agent, and the total amount of the powdery reducing agent added was 1.2 kg.
Example 18: the rutile type titanium dioxide was produced in a similar manner to example 6, except that in this example, 2.5 kg of magnesium powder and 0.5 kg of iron powder were mixed together to form a powdery reducing agent, and the total amount of the powdery reducing agent added was 3.0 kg.
Example 19: the rutile titanium dioxide was prepared in a similar manner to example 8, except that in this example, 3 kg of iron powder and 0.3 kg of carbon powder were mixed together to form a powdery reducing agent, and the total amount of the powdery reducing agent added was 3.5 kg.
Example 20: the rutile titanium dioxide manufacturing method in this example issimilar to example 10, except that in this example, the powdered reducing agent used is a mixture of 3.5 kg of carbon powder, 0.2 kg of zinc powder, 0.2 kg of aluminum powder, 0.2 kg of magnesium powder, and 0.2 kg of iron powder, and the total amount of the powdered reducing agent added is 4.3 kg.
Example 21: the rutile type titanium dioxide was prepared in a similar manner to example 11, except that in this example, 4 kg of a powdery reducing agent was used in combination with 0.2 kg of aluminum powder, 0.2 kg of magnesium powder, and 0.2 kg of iron powder, and the total amount of the powdery reducing agent added was 4.6 kg.
Example 22: the rutile type titanium dioxide was prepared in a similar manner to example 12, except that in this example, 4.5 kg of aluminum powder, 0.2 kg of magnesium powder, and 0.2 kg of iron powder were mixed together to form a powdery reducing agent, and the total amount of the powdery reducing agent added was 4.9 kg.
Example 23: the rutile type titanium dioxide was prepared in a similar manner to example 13, except that in this example, 5 kg of magnesium powder, 0.2 kg of iron powder, and 0.5 kg of carbon powder were mixed to form a powdery reducing agent, and the total amount of the powdery reducing agent added was 5.7 kg.
Example 24: the rutile titanium dioxide was prepared in a similar manner to example 14, except that in this example, 4 kg of iron powder, 0.2 kg of zinc powder, and 0.5 kg of carbon powder were mixed to form the powdery reducing agent, and the total amount of the powdery reducing agent added was 4.7 kg.
Claims (8)
1. A method for preparing rutile titanium dioxide by adding a powdery reducing agent is characterized by comprising the following steps:
(1) adding a powdery reducing agent into a raw material consisting of metatitanic acid or anatase titanium dioxide, and uniformly mixing, wherein the powdery reducing agent is at least one of carbon powder, zinc powder, aluminum powder, magnesium powder and iron powder, and the total amount of the added powdery reducing agent is TiO in the raw material20.5 to 6 percent of net weight;
(2) and (2) heating the material prepared in the step (1) to 820-910 ℃ for calcining, preserving heat for 0.5-5 hours, and naturally cooling to normal temperature to obtain the rutile titanium dioxide.
2. The method as claimed in claim 1, wherein the material obtained in step (1) is dried and ground before being calcined by heating to 820 ℃ to 910 ℃.
3. A method according to claim 1 or 2, characterized in that the powdered reducing agent is carbon powder.
4. The method of claim 2, wherein said powdered reducing agent is zinc powder.
5. The method according to claim 2, wherein the powdery reducing agent is aluminum powder.
6. The method of claim 2, wherein the powdered reducing agent is magnesium powder.
7. The method according to claim 2, characterized in that the powdered reducing agent is iron powder.
8. The method as claimed in claim 2 or 4 or 5 or 6 or 7, wherein in the step (1), metatitanic acid is used as a raw material, the powdery reducing agent at least comprises one of zinc powder, aluminum powder, magnesium powder and iron powder, hydrochloric acid is added into the obtained material after the powdery reducing agent is added and uniformly mixed, the acidity is adjusted to ensure that the pH of the material is less than or equal to 2.0, metatitanic acid and the powdery reducing agent are reacted until the powdery reducing agent is completely disappeared, the pH value of the material is adjusted to be 2.0-4.0 by ammonia water, the material is washed by purified water, chemical analysis is carried out on the material in the washing process, and the washing is stopped when the residual mass percentage content of the powdery reducing agent ions and the weight percentage content of chloride ions introduced by the hydrochloric acid are less than or equal to 0.003%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492851A (en) * | 2011-12-29 | 2012-06-13 | 攀枝花钢城集团有限公司 | Method for smelting and extracting zinc tailings by recovery method |
| CN106526082A (en) * | 2016-11-04 | 2017-03-22 | 四川龙蟒钛业股份有限公司 | Activity detection method of reductive aluminum powder |
| CN106526081A (en) * | 2016-11-04 | 2017-03-22 | 四川龙蟒钛业股份有限公司 | Reduced iron powder activity detection method |
| CN107963657A (en) * | 2018-01-19 | 2018-04-27 | 中国科学院过程工程研究所 | The new method that titanium extracts in a kind of rich-titanium material |
| CN109761599A (en) * | 2019-03-06 | 2019-05-17 | 中国石油大学(华东) | A kind of preparation method and application of the sub- titanium oxide conductivity ceramics of Magn é li phase |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2160230C2 (en) * | 1999-01-10 | 2000-12-10 | Волгоградское открытое акционерное общество "Химпром" | Method of production of titanium dioxide |
| CN1283555C (en) * | 2003-12-03 | 2006-11-08 | 苏州大学 | Method for preparing rutile nano titanium dioxide |
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- 2005-04-27 CN CNB2005100705501A patent/CN1318307C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492851A (en) * | 2011-12-29 | 2012-06-13 | 攀枝花钢城集团有限公司 | Method for smelting and extracting zinc tailings by recovery method |
| CN106526082A (en) * | 2016-11-04 | 2017-03-22 | 四川龙蟒钛业股份有限公司 | Activity detection method of reductive aluminum powder |
| CN106526081A (en) * | 2016-11-04 | 2017-03-22 | 四川龙蟒钛业股份有限公司 | Reduced iron powder activity detection method |
| CN107963657A (en) * | 2018-01-19 | 2018-04-27 | 中国科学院过程工程研究所 | The new method that titanium extracts in a kind of rich-titanium material |
| CN107963657B (en) * | 2018-01-19 | 2019-10-18 | 中国科学院过程工程研究所 | A kind of method that titanium extracts in rich-titanium material |
| CN109761599A (en) * | 2019-03-06 | 2019-05-17 | 中国石油大学(华东) | A kind of preparation method and application of the sub- titanium oxide conductivity ceramics of Magn é li phase |
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