CN1363521A - Process for preparing anatase crystal type nano TiO2 - Google Patents
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- CN1363521A CN1363521A CN 01107022 CN01107022A CN1363521A CN 1363521 A CN1363521 A CN 1363521A CN 01107022 CN01107022 CN 01107022 CN 01107022 A CN01107022 A CN 01107022A CN 1363521 A CN1363521 A CN 1363521A
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Abstract
A process for preparing nano anatase-type TiO2 from meta-titanic acid includes such steps as dissolving in alkali solution to obtain n-titanic acid, dissoving in acid solution to obtain Tio2 sol, coagulating, dewatering, extracting with organic substance, separating TiO2 sol, and calcine. Its advantages include high purity (98% or more) and 5-30 nm of granularity.
Description
The present invention relates to make the preparation method of the nano level anatase crystal type titanium dioxide of photocatalyst, makeup etc.
Anatase crystal type nano TiO 2 is owing to the UV-light in the sunlight being had intensive absorption and the high reaction activity of itself are widely used in making photocatalyst, makeup etc.The external method for preparing anatase crystal type nano TiO 2 mainly contains titanium tetrachloride vapour phase oxidation process, titanyl sulfate or titanium sulfate solution liquid phase water solution, sol-gel method etc.Prepare this kind product with the titanium tetrachloride vapour phase oxidation process and relate to high-temperature reaction process, very high to the erosion resistance requirement of equipment, technical difficulty is big; It is bigger to adopt titanyl sulfate or titanium sulfate solution liquid-phase hydrolysis method to prepare the nano titanium oxide powder footpath that this kind product makes, and generally can only prepare the above nanometer titanium dioxide titanium valve of 30 nanometers (nm), causes the photocatalytic activity of this kind product to reduce greatly; Adopt sol-gel method to prepare this kind product owing to be difficult to accomplish thoroughly separating of titanium colloidal sol and water, make that the nanometer titanium dioxide titanium valve bonding of preparation is serious, the calcining back is difficult to depolymerization, makes that the nanometer titanium dioxide titanium valve dispersiveness of preparation is relatively poor, and particle diameter is bigger.
Given this, the object of the present invention is to provide the preparation method of the anatase crystal type nano TiO 2 that a kind of purity is higher, particle diameter is less.
The present invention makes raw material with metatitanic acid, adopt the positive metatitanic acid of the molten acquisition of alkali, the molten acquisition TiO 2 sol of acid, with flocculation agent TiO 2 sol is condensed with water squeezing and to handle, with extraction agent extracting and separating TiO 2 sol, calcining and decomposing is removed organic impurities such as flocculation agent and extraction agent under the decomposition temperature of selected flocculation agent again, realizes its purpose with the nanometer titanium dioxide titanium valve that obtains anatase crystal type.
The preparation method of anatase crystal type nano TiO 2 of the present invention (referring to accompanying drawing) is characterized in that having the following steps:
(1) the molten metatitanic acid that will have the anatase crystal type microlitic structure of alkali is pulled an oar into TiO
2Concentration is the slurries of 80～200g/l, and it is molten that at least a alkali in adding yellow soda ash, sodium bicarbonate, sodium acetate, sodium ethylate, sodium hydroxide, potassium hydroxide, the Lithium Oxide 98min carries out alkali, TiO
2With with K
2The ratio of the alkali of O meter is 1: 1.5～5.0, is incubated depolymerization 5～8 hours then under 50～100 ℃ temperature.
Raw material metatitanic acid used in the present invention has the microlitic structure of anatase crystal type, and the content of ferric oxide is less than 40ppm.Can select the intermediates of sulfuric acid method titanium pigment factory for use.
This step adds alkali in the slurries of metatitanic acid, has both played to make the metatitanic acid degraded, keeps the original microlitic structure of metatitanic acid again.
(2) washing with the molten material of alkali after filtration, wash to filter cake and be neutral, obtain the positive metatitanic acid of anatase crystal type.
Wash with deionized water or tap water in this step, wherein with better with deionized water.
(3) the molten 1. step acid of acid is molten, and positive metatitanic acid is mixed with slurries, makes TiO
2Concentration be 80～200g/l, after stirring, adding at least a acid in sulfuric acid, Mono Chloro Acetic Acid, chlorsulfonic acid, the phosphoric acid, to carry out acid molten, sour add-on is counted TiO with sulfuric acid
25～10%, subsequently in 60～80 ℃ the reaction 3～4 hours; 2. the acid of two steps is molten, and sour molten gains of a step are warming up to more than 80～90 ℃, and it is molten that acid is carried out at least a acid in adding hydrochloric acid, nitric acid, glacial acetic acid, sulfuric acid, the phosphoric acid, and the add-on of acid is counted TiO with nitric acid
210～30%, constant level reaction 3～5 hours under 80～100 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.
(4) at least a flocculation agent that adds in the colloidal sol of titanium dioxide in this Mierocrystalline cellulose of carboxymethyl, OP emulsifying agent, the cationic polyacrylamide through the ammonium modification, ox glue, polyhexene alcohol, poly-hexylene glycol, the tetramethylolmethane of gel carries out gel, and the add-on of flocculation agent is TiO by weight
23～10%, under 50～80 ℃ temperature, reacted 0.5～1 hour, water flowing is cooled to room temperature, gel.
The molecular weight of the cationic polyacrylamide of ammonium salt modification is 10000～50000 in this step, and polyhexene alcohol molecular weight is 8000～12000, and poly-hexylene glycol molecular weight is 3000～5000.
(5) extraction is put into extractor with gel, extracts with at least a extraction agent in trichloromethane, dithiocarbonic anhydride, ether, naphthene sulfonic acid, the kerosene, then with the extraction phase underpressure distillation, reclaims extraction agent, gets anhydrous TiO 2 sol.
(6) calcining is fired to the flocculation agent decomposition fully with TiO 2 sol under the decomposition temperature of selected flocculation agent, just gets the anatase crystal type nano TiO 2 crude product.
This step adopts calcining and decomposing to remove organic impurities such as flocculation agent.Its calcining temperature is 400～800 ℃, and flocculation agent used under this temperature can decompose fully.
(7) pulverizing is cooled to room temperature with the nano titanium oxide crude product, carries out sand milling, gas powder, makes the anatase crystal type nano TiO 2 product.
This anatase crystal type nano TiO 2 is detected with x-ray diffractometer, scanning electronic microscope, and its particle diameter is 5～30 nanometers, and crystal formation is an anatase titanium dioxide.
Use the nano titanium oxide of the inventive method preparation to can be used for preparing photocatalyst, makeup etc.
The present invention has following obvious advantage and unusual effect compared with prior art.
One, use the steady quality of the nano titanium oxide of the inventive method manufacturing, titanium dioxide purity can reach more than 98%.
Two, because the present invention uses mixing acid, alkali to carry out that acid is molten, alkali is molten, can fully keep the sharp titanium microlitic structure in the metatitanic acid, make the nano titanium oxide that makes be anatase crystal type, the mixed crystal of no rutile.
Three, the dispersiveness of nano titanium oxide in water of using the inventive method to make is strong, and pattern is regular, and is strong to the absorption of UV-light.
Four, using the particle diameter of the nano titanium oxide that the inventive method makes tiny, is 5～30 nanometers.
Five, the inventive method use sulfate process titanium dioxide the intermediates metatitanic acid as raw material, not only cheap, and conveniently be easy to get, other auxiliary material is conventional raw material, buys easily, production cost is lower
Six, do not use the severe condition of High Temperature High Pressure in the inventive method, production process all can be finished at normal temperatures and pressures, and preparation technology is simple, and processing parameter is controlled easily, is easy to large-scale industrial production.
Seven, using the inventive method to prepare in the process of nano titanium oxide, the three wastes are less, and are nontoxic, do not have corrosion, administer easily.
Below, the invention will be further described to use embodiment again.
Brief description of drawings.
Accompanying drawing is the preparation method's of an a kind of anatase crystal type nano TiO 2 of the present invention schema.
Embodiment 1
The preparation method of a kind of anatase crystal type nano TiO 2 of the present invention, its processing step as shown in drawings, its technological process is as follows:
(1) the molten metatitanic acid raw material that will have the anatase crystal type microlitic structure of alkali is pulled an oar into TiO
2Concentration is the slurries of 200g/l, adds that to carry out alkali in the mixed base of yellow soda ash, sodium acetate, three kinds of alkali of sodium hydroxide molten, and the weight ratio of yellow soda ash, sodium acetate, sodium hydroxide is 4: 2: 4, TiO
2With mixed base (with K
2The O meter) ratio is 1: 1.5, and then, the insulation depolymerization is 8 hours under 100 ℃ temperature, and temperature controlling is selected common super constant temperature trough for use.
(2) washing is filtered the molten material of alkali, wash to filter cake and be neutral with B, positive metatitanic acid.
(3) the molten 1. step acid of acid is molten, and positive metatitanic acid is mixed with slurries, makes TiO
2Concentration be 200g/l, after stirring, it is molten that the mixing acid that adds sulfuric acid, two kinds of acid of chlorsulfonic acid carries out acid, the weight ratio of sulfuric acid, chlorsulfonic acid is 2: 8, the amount of adding mixing acid is counted TiO with sulfuric acid
25%, then in 60 ℃ the reaction 4 hours.2. the acid of two steps is molten, and sour molten gains of a step are warming up to 90 ℃, adds the mixing acid of nitric acid, sulfuric acid, three kinds of acid of phosphoric acid (three's weight ratio is 2: 7: 1), and the add-on of mixing acid is counted TiO with nitric acid
210%, back flow reaction 3 hours under 100 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.Common super constant temperature trough is selected in the control of said temperature for use.
(4) the gel mixture that adds this Mierocrystalline cellulose of flocculation agent carboxymethyl, tetramethylolmethane, OP emulsifying agent (three's weight ratio is 4: 2: 4) in the colloidal sol of titanium dioxide condenses, and add-on is TiO by weight
23%, under 80 ℃ temperature, reacted 0.5 hour, with common super constant temperature trough controlled temperature, water flowing is cooled to room temperature, gel.
(5) extraction is put into extractor with gel, extracts with the mixture of extraction agent trichloromethane, naphthene sulfonic acid (weight ratio of the two is 8: 2), with the extraction phase underpressure distillation, reclaims extraction agent, must anhydrous TiO 2 sol.
(6) calcining will be distilled the anhydrous TiO 2 sol of back gained in retort furnace, under 600 ℃ of the decomposition temperatures of this Mierocrystalline cellulose of carboxymethyl, tetramethylolmethane, OP emulsifying agent, be fired to organism such as flocculation agent and extraction agent and decompose fully, just the nano titanium oxide crude product.
(7) pulverize and the nano titanium oxide crude product to be cooled to room temperature to carry out sand milling, carry out the gas powder, make the anatase crystal type nano TiO 2 product with micronizer mill with sand mill.
Through detecting with x-ray diffractometer, scanning electronic microscope, the particle diameter of titanium dioxide powder is 7～15nm, and crystal formation is an anatase crystal type.
The anatase crystal type nano TiO 2 that the method for use present embodiment makes is particularly useful for making photocatalyst and makeup etc.
Embodiment 2
The preparation method of a kind of anatase crystal type nano TiO 2 of the present invention, substantially the same manner as Example 1, the equipment of employing is identical, and its technological process is as follows:
Metatitanic acid is pulled an oar into the slurries that titanium dioxide concentration is 80g/L, add the mixture of sodium bicarbonate, sodium ethylate, Lithium Oxide 98min (three's weight ratio is 4: 4: 2), TiO
2With alkali (with K
2The O meter) ratio is 1: 5.0, is incubated depolymerization 5 hours then under 50 ℃ temperature, and afterwards, it is neutral that filtration washing to filter cake is, and products obtained therefrom is positive metatitanic acid.Positive metatitanic acid is mixed with slurries, makes TiO
2Concentration reach 80g/l, the back that stirs adds Mono Chloro Acetic Acid, phosphoric acid (weight ratio of the two is 8: 2), add-on is counted TiO with sulfuric acid
210%, in 80 ℃ of reactions 3 hours, mixture is warming up to 80 ℃ subsequently then, add the mixture of hydrochloric acid, glacial acetic acid, sulfuric acid (three's weight ratio is 4: 3: 3), add-on is counted TiO with nitric acid
230%, back flow reaction 5 hours under 80 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.Adding in the colloidal sol of above-mentioned titanium dioxide through molecular weight is that the cationic polyacrylamide of 10000～50000 ammonium salt modification, the mixture of ox glue (weight ratio of the two is 5: 5) condense, and add-on is TiO by weight
210%, under 80 ℃ temperature, reacted 1 hour, water flowing is cooled to room temperature.The material that obtains is put into extractor, extract with the mixture of dithiocarbonic anhydride, ether, kerosene (three's weight ratio is 7: 2: 1), extraction agent is reclaimed in the extraction phase underpressure distillation.The material that the distillation back is remaining decomposes fully organism 650 ℃ of calcinings, and products obtained therefrom is cooled to room temperature, adds dispersion agent, carries out sand milling, gas powder, just obtains the anatase crystal type nano TiO 2 product.Products obtained therefrom is anatase crystal type entirely.Particle diameter is 10～20nm.
The anatase crystal type nano TiO 2 that the method for use present embodiment makes is applicable to preparation photocatalyst and makeup etc.
Embodiment 3
The preparation method of a kind of anatase crystal type nano TiO 2 of the present invention, substantially the same manner as Example 1, the equipment of employing is identical, and its technological process is as follows:
Metatitanic acid is pulled an oar into the slurries that titanium dioxide concentration is 140g/L, add sodium hydroxide, TiO
2With alkali (with K
2The O meter) ratio is 1: 3.3, is incubated depolymerization 6.5 hours then under 75 ℃ temperature, and afterwards, it is neutral that filtration washing to filter cake is, and products obtained therefrom is positive metatitanic acid.Positive metatitanic acid is mixed with slurries, makes TiO
2Concentration reach 140g/l, the back that stirs adds Mono Chloro Acetic Acid and carries out acidifying, add-on is counted TiO with sulfuric acid
27.5%, in 70 ℃ of reactions 3.5 hours, mixture is warming up to 85 ℃ subsequently then, add hydrochloric acid, add-on is counted TiO with nitric acid
220%, constant level reaction 4.0 hours under 90 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.Add molecular weight and be the cationic polyacrylamide of 10000～50000 ammonium salt modification in the colloidal sol of above-mentioned titanium dioxide, add-on is TiO by weight
26.5%, under 65 ℃ temperature, reacted 45 minutes, water flowing is cooled to room temperature.The material that obtains is put into extractor, extract with kerosene, extraction agent is reclaimed in the extraction phase underpressure distillation.The remaining material in distillation back is calcined under the decomposition temperature of 620 ℃ of condensation products down to the organism decomposition fully, and products obtained therefrom is cooled to room temperature, adds dispersion agent, carries out sand milling, gas powder, just obtains the anatase crystal type nano TiO 2 product.Products obtained therefrom is hundred-percent anatase crystal type, and particle diameter is 15～30nm.
The anatase crystal type nano TiO 2 that the method for use present embodiment makes is specially adapted to makeup.
Embodiment 4
The preparation method of a kind of anatase crystal type nano TiO 2 of the present invention, substantially the same manner as Example 1, the equipment of employing is identical, and its technological process is as follows:
Metatitanic acid is pulled an oar into the slurries that titanium dioxide concentration is 110g/L, add the mixture of sodium ethylate, potassium hydroxide, Lithium Oxide 98min (three's weight ratio is 2: 7: 1), TiO
2With alkali (with K
2The O meter) ratio is 1: 2.4, is incubated depolymerization 7 hours then under 65 ℃ temperature, and afterwards, it is neutral that filtration washing to filter cake is, and products obtained therefrom is positive metatitanic acid.Positive metatitanic acid is mixed with slurries, makes TiO
2Concentration reach 110g/l, the mixture that the back that stirs adds chlorsulfonic acid, phosphoric acid (weight ratio of the two 9: 1) carries out acidifying, add-on is counted TiO with sulfuric acid
26.0%, in 65 ℃ of reactions 3.2 hours, mixture is warming up to 82 ℃ subsequently then, add the mixture of nitric acid, sulfuric acid (weight ratio of the two is 8: 2), add-on is counted TiO with nitric acid
215%, constant level reaction 4.5 hours under 85 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.Adding OP emulsifying agent, molecular weight are that 8000～12000 polyhexene alcohol, the mixture of tetramethylolmethane (three's weight ratio is 3: 4: 3) condense in the colloidal sol of titanium dioxide, and add-on is TiO by weight
24.5%, under 75 ℃ temperature, reacted 50 minutes, water flowing is cooled to room temperature.The material that obtains is put into extractor, extract,, reclaim extraction agent the extraction phase underpressure distillation with the mixture of kerosene, trichloromethane (weight ratio of the two is 8: 2).The material that the distillation back is remaining is fired to organism at 700 ℃ and decomposes fully, and products obtained therefrom is cooled to room temperature, adds dispersion agent, carries out sand milling, gas powder, just obtains the anatase crystal type nano TiO 2 product.Product is 100% anatase crystal type, and particle diameter is 10～25nm.
The anatase crystal type nano TiO 2 that the method for use present embodiment makes is specially adapted to photocatalyst and makeup.
Embodiment 5
The preparation method of a kind of anatase crystal type nano TiO 2 of the present invention, substantially the same manner as Example 1, the equipment of employing is identical, and its technological process is as follows:
Metatitanic acid is pulled an oar into the slurries that titanium dioxide concentration is 180g/L, add the mixture of yellow soda ash, potassium hydroxide, sodium ethylate (three's weight ratio is 2: 4: 4), TiO
2With alkali (with K
2The O meter) ratio is 1: 4.5, is incubated depolymerization 6 hours then under 90 ℃ temperature, and afterwards, it is neutral that filtration washing to filter cake is, and products obtained therefrom is positive metatitanic acid.Positive metatitanic acid is mixed with slurries, makes TiO
2Concentration reach 180g/l, the mixture that the back that stirs adds sulfuric acid, amine sulfonic acid (weight ratio of the two is 5: 5) carries out acidifying, add-on is counted TiO with sulfuric acid
28.5%, in 75 ℃ of reactions 3.8 hours, mixture is warming up to 88 ℃ subsequently then, add the mixture of hydrochloric acid, phosphoric acid (weight ratio of the two is 9: 1), add-on is counted TiO with nitric acid
225%, constant level reaction 4.5 hours under 95 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.The mixture that adds this Mierocrystalline cellulose of carboxymethyl, OP emulsifying agent, molecular weight and be 3000～5000 poly-hexylene glycol (three's weight ratio is 4: 3: 3) in the colloidal sol of titanium dioxide condenses, and add-on is TiO by weight
38.5%, under 75 ℃ temperature, reacted 50 minutes, water flowing is cooled to room temperature.The material that obtains is put into extractor, extract with the mixture of ether, naphthene sulfonic acid (weight ratio of the two is 3: 7), extraction agent is reclaimed in the extraction phase underpressure distillation.The remaining material in distillation back is fired to organism decomposes fully under 680 ℃, products obtained therefrom is cooled to room temperature, adds dispersion agent, carries out sand milling, gas powder, just obtains the anatase crystal type nano TiO 2 product.Product is hundred-percent anatase crystal type, and particle diameter is 5～15nm.
The anatase crystal type nano TiO 2 that the method for use present embodiment makes is particularly useful for making photocatalyst etc.
Embodiment 6
The preparation method of a kind of anatase crystal type nano TiO 2 of the present invention, substantially the same manner as Example 1, the equipment of employing is identical, and its technological process is as follows:
Metatitanic acid is pulled an oar into the slurries that titanium dioxide concentration is 120g/L, add the mixture of sodium acetate, sodium ethylate, Lithium Oxide 98min (three's weight ratio is 2: 7: 1), TiO
2With alkali (with K
2The O meter) ratio is 1: 2.8, is incubated depolymerization 7 hours then under 70 ℃ temperature, and afterwards, it is neutral that filtration washing to filter cake is, and products obtained therefrom is positive metatitanic acid.Positive metatitanic acid is mixed with slurries, makes TiO
2Concentration reach 100g/l, the back that stirs adds sulfuric acid, Mono Chloro Acetic Acid (weight ratio of the two is 5: 5), add-on is counted TiO with sulfuric acid
28.0%, in 70 ℃ of reactions 3 hours, mixture is warming up to 80 ℃ subsequently then, add the mixture of glacial acetic acid, sulfuric acid (weight ratio of the two is 7: 3), add-on is counted TiO with nitric acid
212%, constant level reaction 5 hours under 88 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.The mixture that adds ox glue, tetramethylolmethane (the heavy ratio of the two is 8: 2) in the colloidal sol of titanium dioxide condenses, and add-on is TiO by weight
24.2%, under 80 ℃ temperature, reacted 50 minutes, water flowing is cooled to room temperature.The material that obtains is put into extractor, extract,, reclaim extraction agent the extraction phase underpressure distillation with dithiocarbonic anhydride.The material that the distillation back is remaining decomposes fully to organism at 500 ℃ temperature lower calcination, and products obtained therefrom is cooled to room temperature, adds dispersion agent, carries out sand milling, gas powder, just obtains the anatase crystal type nano TiO 2 product.Product is hundred-percent anatase crystal type, particle diameter 5～10nm.
The anatase crystal type nano TiO 2 that the method for use present embodiment makes is specially adapted to photocatalyst.
Embodiment 7
The preparation method of a kind of anatase crystal type nano TiO 2 of the present invention, substantially the same manner as Example 1, the equipment of employing is identical, and its technological process is as follows:
Metatitanic acid is pulled an oar into the slurries that titanium dioxide concentration is 150g/L, add the mixture of sodium bicarbonate, sodium ethylate, potassium hydroxide (three's weight ratio is 2: 7: 1), TiO
2With alkali (with K
2The O meter) ratio is 1: 3.7, is incubated depolymerization 6.5 hours then under 85 ℃ temperature, and afterwards, it is neutral that filtration washing to filter cake is, and products obtained therefrom is positive metatitanic acid.Positive metatitanic acid is mixed with slurries, makes TiO
2Concentration reach 90g/l, the mixture that the back that stirs adds chlorsulfonic acid, phosphoric acid (weight ratio of the two is 8: 2) carries out acidifying, add-on is counted TiO with sulfuric acid
28%, in 70 ℃ of reactions 4 hours, mixture is warming up to 90 ℃ subsequently then, add the mixture of hydrochloric acid, glacial acetic acid (weight ratio of the two is 6: 4), add-on is counted TiO with nitric acid
212%, constant level reaction 5 hours under 100 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide.The mixture that adds carboxymethyl cellulose, OP emulsifying agent, tetramethylolmethane (three's weight ratio is 8: 1: 1) in the colloidal sol of titanium dioxide condenses, and add-on is TiO by weight
25%, under 50 ℃ temperature, reacted 35 minutes, water flowing is cooled to room temperature.The material that obtains is put into extractor, extract,, reclaim extraction agent the extraction phase underpressure distillation with trichloromethane.The material that the distillation back is remaining decomposes fully to organism at 720 ℃ temperature lower calcination, and products obtained therefrom is cooled to room temperature, adds dispersion agent, carries out sand milling, gas powder, just obtains the anatase crystal type nano TiO 2 product.Product is hundred-percent anatase crystal type, and particle diameter is 20～30nm.
The anatase crystal type nano TiO 2 that the method for use present embodiment makes is particularly useful for making photocatalyst.
Claims (3)
1, the preparation method of anatase crystal type nano TiO 2 is characterized in that having the following steps:
(1) the molten metatitanic acid that will have the anatase crystal type microlitic structure of alkali is pulled an oar into TiO
2Concentration is the slurries of 80～200g/l, and it is molten that at least a alkali in adding yellow soda ash, sodium bicarbonate, sodium acetate, sodium ethylate, sodium hydroxide, potassium hydroxide, the Lithium Oxide 98min carries out alkali, TiO
2With with K
2The ratio of the alkali of O meter is 1: 1.5～5.0, is incubated depolymerization 5～8 hours then under 50～100 ℃ temperature;
(2) washing with the molten material of alkali after filtration, wash to filter cake and be neutral, obtain positive metatitanic acid;
(3) the molten 1. step acid of acid is molten, and positive metatitanic acid is mixed with slurries, makes TiO
2Concentration be 80～200g/l, after stirring, adding at least a acid in sulfuric acid, Mono Chloro Acetic Acid, chlorsulfonic acid, the phosphoric acid, to carry out acid molten, sour add-on is counted TiO with sulfuric acid
25～10%, subsequently in 60～80 ℃ the reaction 3～4 hours; 2. the acid of two steps is molten, and sour molten gains of a step are warming up to more than 80～90 ℃, and it is molten that acid is carried out at least a acid in adding hydrochloric acid, nitric acid, glacial acetic acid, sulfuric acid, the phosphoric acid, and the add-on of acid is counted TiO with nitric acid
210～30%, constant level reaction 3～5 hours under 80～100 ℃ temperature then, logical water coolant is chilled to below 40 ℃, the colloidal sol of titanium dioxide;
(4) at least a flocculation agent that adds in the colloidal sol of titanium dioxide in carboxymethyl cellulose, OP emulsifying agent, the cationic polyacrylamide through the ammonium salt modification, ox glue, polyhexene alcohol, poly-hexylene glycol, the tetramethylolmethane of gel carries out gel, and the add-on of flocculation agent is TiO by weight
23～10%, under 50～80 ℃ temperature, reacted 0.5～1 hour, water flowing is cooled to room temperature, gel;
(5) extraction is put into extractor with gel, extracts with at least a extraction agent in trichloromethane, dithiocarbonic anhydride, ether, naphthene sulfonic acid, the kerosene, then with the extraction phase underpressure distillation, reclaims extraction agent, gets anhydrous TiO 2 sol;
(6) calcining is fired to flocculation agent and extraction agent with TiO 2 sol and decomposes fully under the decomposition temperature of selected flocculation agent, just the anatase crystal type nano TiO 2 crude product.
(7) pulverizing is cooled to room temperature with the nano titanium oxide crude product, carries out sand milling, gas powder, makes the anatase crystal type nano TiO 2 product.
2, the preparation method of anatase crystal type nano TiO 2 according to claim 1 is characterized in that washing with deionized water or tap water in the said step (2).But it is better with deionized water.
3, the preparation method of anatase crystal type nano TiO 2 according to claim 1 is characterized in that the incinerating temperature is 400～800 ℃ in the said step (6).Flocculation agent used under this temperature can both decompose fully.
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| CN100438973C (en) * | 2007-09-29 | 2008-12-03 | 中国科学院山西煤炭化学研究所 | Method for preparing TiO2 visible light photocatalyst |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326777C (en) * | 2003-04-10 | 2007-07-18 | 广州市华之特奥因特种材料科技有限公司 | Preparation method of titanium oxide and its application |
| CN100445209C (en) * | 2005-07-28 | 2008-12-24 | 同济大学 | Preparation method of new type nano-titanium dioxide powder |
| CN100482748C (en) * | 2006-03-03 | 2009-04-29 | 攀钢集团攀枝花钢铁研究院 | Preparation method of high-water-dispersibility titanium dioxide |
| CN100438973C (en) * | 2007-09-29 | 2008-12-03 | 中国科学院山西煤炭化学研究所 | Method for preparing TiO2 visible light photocatalyst |
| CN101559358B (en) * | 2008-04-15 | 2011-06-01 | 李志宏 | Technique for improving visible light catalytic activity of titanium dioxide photocatalyst |
| CN104261469A (en) * | 2014-10-21 | 2015-01-07 | 福州大学 | Titanium dioxide as well as preparation method and application thereof |
| CN104261469B (en) * | 2014-10-21 | 2015-11-18 | 福州大学 | A kind of titanium dioxide and its preparation method and application |
| CN104477981A (en) * | 2014-12-11 | 2015-04-01 | 山东东佳集团股份有限公司 | Preparation method of high-purity titanium dioxide |
| CN112438274A (en) * | 2020-04-03 | 2021-03-05 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN111943262A (en) * | 2020-08-24 | 2020-11-17 | 山西银圣科技有限公司 | Preparation method of titanium dioxide special for oriented silicon steel |
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