CN114573022A - Method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalyst - Google Patents

Method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalyst Download PDF

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CN114573022A
CN114573022A CN202210254361.3A CN202210254361A CN114573022A CN 114573022 A CN114573022 A CN 114573022A CN 202210254361 A CN202210254361 A CN 202210254361A CN 114573022 A CN114573022 A CN 114573022A
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titanium dioxide
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范国利
刘恒
孙智
李峰
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Beijing University of Chemical Technology
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Abstract

The invention discloses a method for preparing high-purity nano titanium dioxide by resource utilization of a waste titanium dioxide-based catalyst, which comprises the following steps: preparing a reaction solution; (II) alkaline hydrolysis reaction; (III) acidolysis reaction; (IV) roasting treatment and the like. The invention utilizes the enhanced mixing and reaction capability in the three-stage emulsifying device, removes impurity metal components in the catalyst by water washing, acid hydrolysis and alkaline hydrolysis reaction to obtain high-purity sodium titanate, and performs acid hydrolysis on the sodium titanate to obtain high-purity nano titanium dioxide, wherein the indexes of the particle size, the purity and the impurity content of the product all meet the standard of GB/T19591-2004 nano titanium dioxide. The method is simple to operate, short in process flow and easy for large-scale production, and provides an important way for resource utilization of the waste titanium dioxide-based catalyst and preparation of a high-purity nano titanium dioxide product.

Description

Method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalyst
Technical Field
The invention belongs to the field of titanium dioxide preparation, and particularly relates to a method for preparing high-purity nano titanium dioxide by resource utilization of a waste titanium dioxide-based catalyst.
Background
Titanium dioxide, commonly known as titanium dioxide, exists in nature in the form of three crystal mineral forms of rutile, brookite and anatase, has wide application due to the characteristics of low price, low toxicity, stable chemical property, excellent photoelectric property and the like, and is a necessary industrial raw material in the fields of coating, plastics, papermaking, rubber, catalysis and the like. China is the largest world titanium dioxide producing country and consuming country, and the reserves of ilmenite of China are the first place in the world. At present, the traditional production process of titanium dioxide comprises a sulfuric acid method and a chlorination method, wherein the sulfuric acid method is listed in the restriction item of the industrial structure adjustment guidance catalog, the proportion of the titanium dioxide produced by the chlorination method reaches 56 percent, and the chlorination method has high requirements on the quality of raw materials and needs to be imported from abroad in large quantity. Therefore, the state places great importance on the development of the titanium dioxide industry, the science and technology department sets a key special item of 'strategic mineral resource development and utilization', the industrialization of the new technology for high-value utilization of the titanium ore resource and the comprehensive utilization of the titanium resource are actively promoted, the titanium dioxide is brought into the national strategic resource storage in the future, and the development of the titanium dioxide industry is further promoted.
Titanium dioxide is a catalyst and catalyst carrier with excellent performance, and has important application in various catalytic fields. At present, the titanium dioxide-based photocatalytic material applied in the fields of water pollution treatment, volatile organic matter removal, photolysis water hydrogen production and oxygen production accounts for about 70 percent of the total amount of the photocatalyst; in the aspect of air pollution treatment, the proportion of the titanium dioxide-based catalytic material is higher by 90 percent. With the increase of the proportion of green hydrogen energy in energy consumption and the increase of the national environmental pollution prevention and control force, the using amount of the titanium dioxide-based catalyst and the total amount of the waste titanium dioxide-based catalyst are increased year by year, about 20 ten thousand tons of waste titanium dioxide-based catalyst are generated every year, the content of titanium dioxide is about 18 ten thousand tons, the waste titanium dioxide-based catalyst often contains components such as precious metals, heavy metals and the like and is listed as dangerous solid waste, if the waste titanium-based catalyst is not treated, the harm to the environment and the health of people is caused, and meanwhile, the great waste of titanium resources and valuable metal resources is caused, which is contrary to the national relevant policy requirements on benign development of the titanium industry chain and comprehensive and efficient utilization of resources. Therefore, a recycling system and an industrial chain of the waste titanium dioxide-based catalyst are established, high-value conversion of valuable metal resources and titanium resources in the waste catalyst is realized, the processing and utilization level of the waste titanium dioxide-based catalyst is improved, and the method has great market value.
At present, few articles and patent reports about the resource utilization of waste titanium dioxide-based catalysts to prepare high-purity nano titanium dioxide exist, and related patents are mostly concentrated in the field of regeneration and utilization of denitration catalysts. The patent (CN 111468103B) discloses a method for preparing a new SCR catalyst by recycling waste SCR denitration catalysts, which comprises the steps of cleaning and filtering the waste SCR denitration catalysts by using an acid cleaning solution, then carrying out acidolysis reaction in sulfuric acid, filtering acidolysis slurry, hydrolyzing and recycling filtrate to obtain ammonium metavanadate, drying and roasting filter cakes to obtain titanium tungsten powder, and preparing the new SCR denitration catalyst by using the obtained ammonium metavanadate and titanium tungsten powder, wherein the method does not relate to the preparation of a high-purity titanium dioxide nano material. Therefore, a simple and efficient method is created to convert the waste titanium dioxide-based catalyst into high-purity nano titanium dioxide for the aspects of rubber, plastics, pesticides, papermaking, daily chemicals and the like, so that the method is not only beneficial to reducing the problems of environmental pollution and high energy consumption caused by the exploitation of titanium ores, but also accords with the national policies related to the circular economic development and the energy conservation and environmental protection, and has double benefits on the economic development and the energy conservation and environmental protection.
Disclosure of Invention
The invention is provided for overcoming the defects in the prior art, and aims to provide a method for preparing high-purity nano titanium dioxide by utilizing waste titanium dioxide-based catalysts in a resource manner.
The invention is realized by the following technical scheme:
a method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalysts comprises the following steps:
preparation of reaction solution
Dispersing the pretreated leaching residues in an alkali solution to form a suspension; the leaching residue is a solid phase left after the waste titanium dioxide-based catalyst is washed and pickled to remove metal components such as noble metal, heavy metal, transition metal and the like in the catalyst, and the main component of the leaching residue is titanium dioxide and possibly contains a small amount of silicon and aluminum components;
(II) alkaline hydrolysis reaction
Adding the suspension obtained in the step (I) into a reactor for alkaline hydrolysis reaction, so that impurity components such as silicon, aluminum and the like in leaching residues are quickly converted into corresponding soluble salts, and centrifuging and washing to obtain an intermediate of high-purity solid-phase titanate;
(III) acid hydrolysis reaction
Mixing the high-purity solid-phase titanate obtained in the step (II) with an acid solution to form a suspension, adding the suspension into a reactor, realizing rapid acidolysis of the titanate by utilizing forced micromixing and reaction strengthening capability in a confined space, and centrifuging, washing and drying after the reaction is finished to obtain nano hydrated titanium dioxide;
(IV) calcination treatment
And (3) roasting the water and the titanium dioxide obtained in the step (III), and naturally cooling to room temperature after roasting to obtain a white solid, namely the nano titanium dioxide.
In the technical scheme, the alkali in the step (I) is any one or more of mixed alkali of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the mass percentage of the alkali in the alkali solution is 15-40%; and (3) the mass percentage of the leaching residue in the suspension liquid in the step (I) is 5-30%.
In the technical scheme, the acid in the step (III) is any one or more of sulfuric acid, hydrochloric acid or acetic acid, and the mass percentage of the acid in the acid solution is 15-20%; and (3) the mass percentage of the high-purity solid-phase titanate in the suspension liquid in the step (III) is 5-20%.
In the above technical solution, the drying conditions in the step (iii) are as follows: drying for 6-12 h at 60-100 ℃.
In the above technical solution, the conditions of the roasting treatment in the step (iv) are as follows: roasting for 2-4 h at 300-500 ℃, and setting the heating rate at 2-10 ℃/min.
In the above technical scheme, the reactors in steps (ii) and (iii) are both three-stage emulsification devices, and the three-stage emulsification devices may be three-stage high shear emulsification machines of wuxi river automation technology ltd.
In the technical scheme, the rotor speed of the reactor in the step (II) is 2000 rad/min-6000 rad/min, and the rotation reaction time is 10 min-60 min; the rotating speed of the rotor of the reactor in the step (III) is 2000rad/min to 6000rad/min, and the rotating reaction time is 10min to 30 min.
A nano titanium dioxide, which is prepared by a method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalysts.
In the technical scheme, the high-purity nano titanium dioxide is pure-phase anatase titanium dioxide, and the particle size is 20-90 nm; ICP (inductively coupled plasma) detection of titanium dioxide content in product>96.8% and Si content<0.05%, aluminum content<0.01 percent; the pH value of the product is 6.5-7.6, and the specific surface area is 120-380 m2(ii) a bulk density of 0.35 to 0.49g/cm3(ii) a The product is white in appearance and white in whiteness>92. The particle size, purity and impurity content of the product all meet the standard of GB/T19591-2004 nanometer titanium dioxide.
The invention has the beneficial effects that:
the invention provides a method for preparing high-purity nano titanium dioxide by utilizing waste titanium dioxide-based catalyst in a recycling manner, which utilizes the functions of crushing, depolymerization, dispersion, mixing enhancement and reaction of a three-stage emulsifying device to realize the crushing of waste titanium dioxide-based catalyst particles, the uniform dispersion in acid-base leachate and the synchronous reaction with the acid-base leachate, thereby improving the separation efficiency of noble metal, heavy metal components and titanium dioxide components in the catalyst and reducing the corrosion of acid-base reaction liquid to equipment and pipelines; the high-efficiency synergy of the high-pressure liquid film shearing, high-frequency oscillation and strong turbulence in the three-stage emulsifying device inhibits the deposition and coating of insoluble/slightly soluble salts on the surfaces of catalyst particles, the uneven local concentration and mass distribution, the agglomeration and secondary crystallization among the particles in the acidolysis and alkaline hydrolysis processes; the contactability and the reactivity of a solid/liquid interface in the suspension are enhanced, and the controllability of acidolysis and alkaline hydrolysis processes of the waste titanium dioxide and the catalyst and the batch stabilization preparation of the high-purity nano titanium dioxide are realized; in the invention, the suspension slurry is injected into the three-stage emulsifying device for intensive mixing and reaction, and compared with the existing kettle type reactor and related processes, the operation is simple, the process flow is short, and batch stable production is easy; meanwhile, the equipment is simple, the cost for preparing the nano titanium dioxide is low, the energy consumption is low, the industrialization prospect is good, and an important way is provided for preparing the nano titanium dioxide by high-valued conversion of the waste titanium dioxide based catalyst.
Drawings
FIG. 1 is an XRD pattern of nano-titania prepared according to examples 1-5 of the present invention (where a is the product of example 1, b is the product of example 2, c is the product of example 3, d is the product of example 4, e is the product of example 5, and f is the titania phase standard card PDF # 78-2486);
FIG. 2 is a scanning electron micrograph of the nano titanium dioxide prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of the nano titanium dioxide prepared in example 2 of the present invention;
FIG. 4 is a scanning electron micrograph of the nano titanium dioxide prepared in example 3 of the present invention;
FIG. 5 is a particle size distribution diagram of nano-titanium dioxide prepared in example 1 of the present invention;
FIG. 6 is a particle size distribution diagram of nano-titanium dioxide prepared in example 5 of the present invention;
FIG. 7 is a physical adsorption isotherm of the nano-titania prepared in example 5 of the present invention;
FIG. 8 shows the appearance and color values of the nano-sized titanium dioxide prepared in examples 1 to 5 of the present invention (wherein a is the product of example 1, b is the product of example 2, c is the product of example 3, d is the product of example 4, and e is the product of example 5);
for a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical scheme of the invention better understood by those skilled in the art, the method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalyst according to the invention is further described by the specific embodiments in combination with the drawings of the specification.
Example 1
A. 40g of leaching residue is dispersed in a sodium hydroxide solution consisting of 200mL of deionized water and 130g of sodium hydroxide, wherein the mass percentage of the sodium hydroxide is 39.39%, and the solid content of the leaching residue in the slurry is 10.8%.
B. And (3) adding the slurry in the step A into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 4000rad/min, rotating for 1h to quickly convert impurity components such as silicon, aluminum and the like in leaching residues into corresponding soluble salts, and centrifuging and washing to obtain the intermediate of the high-purity solid-phase sodium titanate.
C. 24mL of concentrated sulfuric acid with the mass percentage content of 98% is measured and diluted by adding 160mL of deionized water, and the mass percentage content of sulfuric acid in the sulfuric acid solution is 21.20%.
D. Mixing the high-purity solid-phase sodium titanate obtained in the step B with the acid solution obtained in the step C to form a suspension, adding the suspension into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 4000rad/min, rotating for 1h and 30min, realizing rapid acidolysis of the sodium titanate by utilizing forced micro-mixing and reaction strengthening capacity in a confined space, and obtaining the nano hydrated titanium dioxide by centrifuging, washing and drying at 60 ℃ for 12 h.
E. And D, roasting the water and the titanium dioxide obtained in the step D at 500 ℃ for 4 hours, setting the heating rate at 10 ℃/min, and naturally cooling to room temperature to obtain a white solid, namely the nano titanium dioxide.
The product yield is 95.2%, a in fig. 1 shows that the product is anatase titanium dioxide with a single crystal phase, and the scanning electron micrograph of fig. 2 shows that the nano titanium dioxide has uniform particle size, and the particle size is about 70 nm; ICP (inductively coupled plasma) detection of titanium dioxide content in product>96.2%, silicon content<0.04%, aluminum content<0.008 percent; the pH value of the product is 7.1, and the specific surface area is 292m2(ii)/g, bulk density of 0.4631g/cm3(ii) a As can be seen from FIG. 6, the particle size of the product was D as measured by laser particle size test10＝38nm，D50＝81nm，D90379 nm. The product is seen in fig. 8 a as white in appearance and having a whiteness of 92.5.
Example 2
A. And (3) dispersing 20g of leaching residues in a sodium hydroxide solution consisting of 200mL of deionized water and 130g of sodium hydroxide, wherein the mass percentage of the sodium hydroxide is 39.39%, and the solid content of the leaching residues in the slurry is 5.7%.
B. And (3) adding the slurry in the step A into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 6000rad/min, rotating for 2 hours to quickly convert impurity components such as silicon, aluminum and the like in leaching slag into corresponding soluble sodium salts, and centrifuging and washing to obtain the intermediate of the high-purity solid-phase sodium titanate.
C. 24mL of concentrated sulfuric acid with the mass percentage of 98% is measured and added with 160mL of deionized water for dilution, and the mass percentage of sulfuric acid in the sulfuric acid solution is 21.20%.
D. Mixing the high-purity solid-phase sodium titanate obtained in the step B with the acid solution obtained in the step C to form a suspension, adding the suspension into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 6000rad/min, rotating for 1h, realizing rapid acidolysis of the sodium titanate by utilizing forced micromixing and reaction strengthening capacity in a confined space, centrifuging, washing, and drying at 60 ℃ for 12h to obtain the nano hydrated titanium dioxide.
E. And D, roasting the water and the titanium dioxide obtained in the step D at 500 ℃ for 4 hours, setting the heating rate at 10 ℃/min, and naturally cooling to room temperature to obtain a white solid, namely the nano titanium dioxide.
The product yield is 93.7%, b in fig. 1 shows that the product is anatase titanium dioxide with a single crystal phase, and the scanning electron micrograph in fig. 3 shows that the nano titanium dioxide has uniform particle size, and the particle size is about 40 nm; ICP (inductively coupled plasma) detection of titanium dioxide content in product>96.8%, silicon content<0.05%, aluminum content<0.01 percent; the pH value of the product is 7.2, and the specific surface area is 225m2(ii)/g, bulk density of 0.4256g/cm3(ii) a The particle size of the product is detected to be D by laser particle size test10＝45nm，D50＝75nm，D90420 nm. See b in FIG. 8The product is white in appearance and the whiteness is 100.3.
Example 3
A. And (3) dispersing 20g of leaching residues in a sodium hydroxide solution consisting of 200mL of deionized water and 130g of sodium hydroxide, wherein the mass percentage of the sodium hydroxide is 39.39%, and the solid content of the leaching residues in the slurry is 5.7%.
B. And (3) adding the slurry in the step A into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 5000rad/min, rotating for 2 hours to quickly convert impurity components such as silicon, aluminum and the like in leaching residues into corresponding soluble sodium salts, and centrifuging and washing to obtain the intermediate of the high-purity solid-phase sodium titanate.
C. 24mL of concentrated sulfuric acid with the mass percentage content of 98% is measured and diluted by adding 160mL of deionized water, and the mass percentage content of sulfuric acid in the sulfuric acid solution is 21.20%.
D. Mixing the high-purity solid-phase sodium titanate obtained in the step B with the acid solution obtained in the step C to form a suspension, adding the suspension into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 5000rad/min, rotating for 2 hours, realizing rapid acidolysis of the sodium titanate by utilizing forced micromixing and reaction strengthening capacity in a confined space, centrifuging, washing, and drying at 60 ℃ for 12 hours to obtain the nano hydrated titanium dioxide.
E. And D, roasting the water and the titanium dioxide obtained in the step D at 500 ℃ for 4 hours, setting the heating rate at 10 ℃/min, and naturally cooling to room temperature to obtain a white solid, namely the nano titanium dioxide.
The product yield is 94.2%, the product is anatase titanium dioxide with a single crystal phase as shown in c in fig. 1, and the scanning electron micrograph of fig. 4 shows that the nano titanium dioxide has uniform particle size, and the particle size is about 20 nm; ICP (inductively coupled plasma) detection of titanium dioxide content in product>97.3%, silicon content<0.05%, aluminum content<0.01 percent; the pH value of the product is 7.5, and the specific surface area is 320m2(ii)/g, bulk density of 0.4822g/cm3(ii) a The particle size of the product is D by laser particle size test10＝35nm，D50＝62nm，D90625 nm. It can be seen from c of fig. 8 that the product is white in appearance and has a whiteness of 100.6.
Example 4
A. 40g of leaching residue is dispersed in a potassium hydroxide solution consisting of 200mL of deionized water and 130g of potassium hydroxide, wherein the mass percentage of the potassium hydroxide is 39.39%, and the solid content of the leaching residue in the slurry is 10.8%.
B. And (3) adding the slurry in the step A into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 5000rad/min, rotating for 2 hours to enable impurity components such as silicon, aluminum and the like in leaching slag to be rapidly converted into corresponding soluble potassium salt, and centrifuging and washing to obtain the intermediate of the high-purity solid-phase potassium titanate.
C. 24mL of concentrated sulfuric acid with the mass percentage content of 98% is measured and diluted by adding 160mL of deionized water, and the mass percentage content of sulfuric acid in the sulfuric acid solution is 21.20%.
D. Mixing the high-purity solid-phase potassium titanate obtained in the step B with the acid solution obtained in the step C to form a suspension, adding the suspension into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 5000rad/min, rotating for 1h, realizing rapid acidolysis of the potassium titanate by utilizing forced micromixing and reaction strengthening capacity in a confined space, centrifuging, washing, and drying at 60 ℃ for 12h to obtain the nano hydrated titanium dioxide.
E. And D, roasting the water and the titanium dioxide obtained in the step D at 500 ℃ for 4 hours, setting the heating rate at 10 ℃/min, and naturally cooling to room temperature to obtain a white solid, namely the nano titanium dioxide.
The product yield is 94.3%, and it can be known from d in fig. 1 that the product is anatase titanium dioxide of a single crystal phase, the particle size of the nano titanium dioxide is uniform, and the particle size is about 60 nm; ICP (inductively coupled plasma) detection of titanium dioxide content in product>95.6%, silicon content<0.04%, aluminum content<0.01 percent; the product has pH of 6.9 and specific surface area of 262m2Per gram, bulk density 0.4139g/cm3(ii) a The particle size of the product is detected to be D by laser particle size test10＝68nm，D5098nm, and 165nm for D90. The product is seen in fig. 8 d as white in appearance with a whiteness of 101.8.
Example 5
A. And (3) dispersing 20g of leaching residue in a potassium hydroxide solution consisting of 200mL of deionized water and 130g of potassium hydroxide, wherein the mass percentage of the potassium hydroxide is 39.39%, and the solid content of the waste catalyst in the slurry is 5.7%.
B. And (3) adding the slurry in the step A into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 6000rad/min, rotating for 2 hours to quickly convert impurity components such as silicon, aluminum and the like in leaching slag into corresponding soluble potassium salt, and centrifuging and washing to obtain the high-purity solid-phase potassium titanate intermediate.
C. 20mL of 99.8 mass percent acetic acid is measured and diluted by adding 160mL of deionized water, and the mass percent of the acetic acid in the acetic acid solution is 11.60 percent.
D. Mixing the high-purity solid-phase sodium titanate obtained in the step B with the acid solution obtained in the step C to form a suspension, adding the suspension into a three-stage emulsifying device, setting the rotating speed of a rotor of the reactor to be 6000rad/min, rotating for 1h, realizing rapid acidolysis of potassium titanate by utilizing forced micromixing and reaction capacity enhancement in a confined space, centrifuging, washing, and drying at 60 ℃ for 12h to obtain the nano hydrated titanium dioxide.
E. And D, roasting the water and the titanium dioxide obtained in the step D at 500 ℃ for 4 hours, setting the heating rate at 10 ℃/min, and naturally cooling to room temperature to obtain a white solid, namely the nano titanium dioxide.
The product yield is 95.1%, and the product is anatase titanium dioxide with a single crystal phase as shown in e in figure 1, wherein the nano titanium dioxide has uniform particle size of about 80 nm; ICP (inductively coupled plasma) detection of titanium dioxide content in product>97.6%, silicon content<0.05%, aluminum content<0.01 percent; the pH value of the product was 7.6, and as can be seen from FIG. 8, the specific surface area was 225m2(ii)/g, bulk density of 0.3952g/cm3(ii) a As can be seen from FIG. 7, the particle size of the product was D as measured by laser particle size test10＝52nm，D50＝86nm，D90195 nm. The product is seen in fig. 8 e as white in appearance with a whiteness of 102.2.
The working principle of the method of the invention is as follows:
the method comprises the steps of utilizing a three-stage emulsifying device as process strengthening equipment and means, carrying out alkaline hydrolysis reaction on pretreated leaching residues and alkali liquor in the three-stage emulsifying device, realizing high-efficiency separation of components such as silicon, aluminum and the like through forced micro-mixing and reaction strengthening effect in a confined space to obtain high-purity titanate, carrying out acidolysis on the high-purity titanate and an acid solution in the three-stage emulsifying device to obtain nano-scale hydrated titanium dioxide with narrow particle size distribution, and finally roasting to obtain a high-purity nano titanium dioxide product, wherein the particle size, purity and impurity content indexes of the product all meet the standard of GB/T19591-2004 nano titanium dioxide.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalyst is characterized by comprising the following steps: the method comprises the following steps:
preparation of reaction solution
Dispersing the pretreated leaching residues in an alkali solution to form a suspension;
(II) alkaline hydrolysis reaction
Adding the suspension obtained in the step (I) into a reactor for alkaline hydrolysis reaction, so that impurity components in leached residues are quickly converted into corresponding soluble salts, and centrifuging and washing to obtain high-purity solid-phase titanate;
(III) acid hydrolysis reaction
Mixing the high-purity solid-phase titanate obtained in the step (II) with an acid solution to form a suspension, adding the suspension into a reactor, realizing rapid acidolysis of the high-purity solid-phase titanate by utilizing forced micromixing and reaction strengthening capability in a confined space, and centrifuging, washing and drying after the reaction is finished to obtain nano hydrated titanium dioxide;
(IV) calcination treatment
And (3) roasting the nano water obtained in the step (III) and titanium dioxide, and naturally cooling to room temperature after roasting to obtain a white solid, namely the nano titanium dioxide.
2. The method for preparing high-purity nano titanium dioxide by resource utilization of the waste titanium dioxide-based catalyst according to claim 1, which is characterized in that: the leaching residue is a solid phase left after the metal components in the catalyst are removed by washing and pickling the waste titanium dioxide-based catalyst.
3. The method for preparing high-purity nano titanium dioxide by resource utilization of the waste titanium dioxide-based catalyst according to claim 1, which is characterized in that: the alkali in the step (I) is any one or mixture of more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the mass percentage of the alkali in the alkali solution is 15-40%; and (3) the mass percentage of the leaching residue in the suspension liquid in the step (I) is 5-30%.
4. The method for preparing high-purity nano titanium dioxide by resource utilization of the waste titanium dioxide-based catalyst according to claim 1, which is characterized in that: the acid in the step (III) is one or a mixture of sulfuric acid, hydrochloric acid or acetic acid, and the mass percentage of the acid in the acid solution is 15-20%; and (3) the mass percentage of the high-purity solid-phase titanate in the suspension liquid in the step (III) is 5-20%.
5. The method for preparing high-purity nano titanium dioxide by resource utilization of the waste titanium dioxide-based catalyst according to claim 1, which is characterized in that: the drying conditions in the step (III) are as follows: drying for 6-12 h at 60-100 ℃.
6. The method for preparing high-purity nano titanium dioxide by resource utilization of the waste titanium dioxide-based catalyst according to claim 1, which is characterized in that: the roasting treatment conditions in the step (IV) are as follows: roasting for 2-4 h at 300-500 ℃, and setting the heating rate at 2-10 ℃/min.
7. The method for preparing high-purity nano titanium dioxide by resource utilization of the waste titanium dioxide-based catalyst according to claim 1, which is characterized in that: and (II) and (III) in the step (II) and the step (III), the reactors are three-stage emulsification devices.
8. The method for preparing high-purity nano titanium dioxide by resource utilization of the waste titanium dioxide-based catalyst according to claim 7, which is characterized in that: the rotating speed of the rotor of the reactor in the step (II) is 2000 rad/min-6000 rad/min, and the rotating reaction time is 10 min-60 min; the rotating speed of the rotor of the reactor in the step (III) is 2000rad/min to 6000rad/min, and the rotating reaction time is 10min to 30 min.
9. A high-purity nano titanium dioxide is characterized in that: prepared by the process of any one of claims 1 to 8.
10. The high purity nano titanium dioxide as claimed in claim 9, wherein: the high-purity nano titanium dioxide is pure phase anatase titanium dioxide, and the particle size is 20-90 nm; ICP (inductively coupled plasma) detection of titanium dioxide content in high-purity nano titanium dioxide>96.8%, silicon content<0.05%, aluminum content<0.01 percent; the pH value of the high-purity nano titanium dioxide is 6.5-7.6, and the specific surface area is 120m2/g～380m2(g) bulk density of 0.35g/cm3～0.49g/cm3(ii) a The product is white in appearance and white in whiteness>92。
CN202210254361.3A 2022-03-15 2022-03-15 Method for preparing high-purity nano titanium dioxide by resource utilization of waste titanium dioxide-based catalyst Pending CN114573022A (en)

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