CN1032585C - Preparation for super fine powder of titanium dioxide - Google Patents
Preparation for super fine powder of titanium dioxide Download PDFInfo
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- CN1032585C CN1032585C CN 94111732 CN94111732A CN1032585C CN 1032585 C CN1032585 C CN 1032585C CN 94111732 CN94111732 CN 94111732 CN 94111732 A CN94111732 A CN 94111732A CN 1032585 C CN1032585 C CN 1032585C
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- tio
- titanium dioxide
- fine powder
- super fine
- reaction
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Abstract
The present invention discloses a method for producing special (high-purity) superfine powder of titanium dioxide, which uses TiCl4 as a basic raw material. The method comprises the following steps: adding quantitative alcohol and leading in ammonia gas to a mixed solution prepared from TiCl4 and a nontoxic organic solvent according to a weight ratio, adding quantitative additive and mixing uniformly after a reaction in a pot capable of controlling the pressure and the temperature, adding high purity water for hydrolysis on condition that the additive exists, then calcining and grinding under a specified condition after concentrating and drying, and thereby obtaining the qualified finished product. The method has the advantages of reasonable technology, organic continuous production, nontoxic operation, energy and raw material saving, cost reduction and realization of industrial mass production.
Description
The present invention is a kind of manufacture method of super fine powder of titanium dioxide, particularly at innoxious solvent, adds to depress and carries out.
The existing method for preparing high-purity superfine titanium dioxide adopts alkoxide process more, and does not form the integrated artistic of organic connection, at first with TiCL
4Being raw material, is solvent with toluene and No. 120 solvent oils, mixes and leads to ammonia with ethanol and react, and removes NH after filtration
4CL and distill solvent, the intermediate titanate, then, be raw material with the titanate again, be hydrolyzed, hydrolysis temperature requires very strict, last drying calcining, pulverize and TiO
2Finished product, the disadvantage of this method is:
1. technology is discontinuous, and the synthesising reacting time of intermediate titanate is long.2. must remove solvent through distillation, obtain pure intermediate titanate.3. must fast titanate be dissolved in earlier behind the dehydrated alcohol again with water/ethanol system hydrolysis, hydrolysis concentration is low, will expend plenty of time and energy when concentrated, also has a large amount of ethanol losses simultaneously, and flower is calculated economically, is difficult to suitability for industrialized production.4. because of additive-free adding TiO
2Granularity, monodispersity and sintering character are bad, and be of poor quality.
Nineteen ninety " Huadong Chemical College journal " deliver " hydrolysis of alcoxyl titanium prepares TiO
2Ultrafine particle article and CN1089236A disclosed " high purity monodisperse titanium dioxide micropowder preparing process " are the representative of above-mentioned prior art.
The objective of the invention is transformation to prior art, adopt the reaction under the sealing pressurized conditions of inert non-toxic organic solvent to reach the holistic approach of organic connections of hydrolysis formation in the presence of additive, has nontoxic production, technology is reasonable, improve work efficiency, reduce cost, good product quality and the industrial advantage of realization have overcome the shortcoming that prior art exists.
Technical scheme of the present invention is with TiCL
4Be basic raw material, it is joined with it is to become mixing solutions in inertia carbon, hydrogen, the nitrogen organic solvent.This solvent is the gasoline of aliphatic saturated hydrocarbon, pyridine and derivative thereof, ethers, lightweight Valelinum Liquidum, no inorganic composition and wherein a kind of or its mixture of naphthenic hydrocarbon.TiCL
4With the weight ratio of organic solvent be 1: 2.7-18.In mixing liquid, add alcohols (chemical pure), and feed ammonia gas react generation titanic acid ester and solid sediment NH
4CL.This reaction is to carry out in the encloses container that can control its reaction pressure＜16Kg.The add-on of alcohols is TiCL
44.5～6.5 times of mol, reaction is controlled at below 75 ℃, gets final product termination reaction when the pH value of measuring＞7.Remove NH through separation
4Cl adds additive in remaining parting liquid, its consumption is TiCl
40.01～25% (weight).Normal temperature adds high purity water down, and constantly stirs the reaction that was hydrolyzed in 3-30 minutes, generates molten gelationus TiO2 hydrate.TiCl
4With the weight ratio of water be 1: 0.4～8.Anhydrate the TiO2 hydrate that obtains wetting and alcohol solution through concentrating to remove.Last drying, calcining and pulverizing and make white high-purity superfine titanium dioxide powder finished product.Drying temperature is up to 180 ℃.Calcining is under the oxidizing atmosphere condition, adopts TiO
2Do not produce in the material equipment of pollution and carry out, calcining temperature is 580 ℃～1200 ℃, and calcination time is 0.5-3 hours.Equally, pulverizing also is to adopt TiO
2Do not produce the equipment of pollution.
The encloses container that can control reaction pressure is the reactor that automatically controlled valve is housed in the top, and reaction pressure is controlled at＜2kg.Simultaneously, also being provided with the portion within it that is connected with reactor by control valve is equipped with and can absorbs volatilization gas (NH in the still
3, HCl, organic solvent and alcohols) encloses container of solvent.
Employed alcohols is ethanol, propyl alcohol, Virahol, butanols, amylalcohol and primary isoamyl alcohol a kind of or its mixing liquid wherein.Methyl alcohol is also available, just will increase facility investment.
Adding additive is one of very crucial operation among the present invention.Used additive is that alkane hydroxyl fiber base, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose, Glacial acetic acid, polypropylene acid, polyvinyl alcohol, quadrol, polymaleic acid, nonionic surfactants OP, song draw the wherein any of ketone X-100 and trolamine and the compound material of poly-di-alcohol.
Concentrating is to adopt ultrafiltration membrance filter or reduction vaporization, mainly is in order to remove liquid phase.
Drying is to adopt boulton process or freeze-drying, its drying temperature＜160 ℃.
Calcining temperature is preferably between 720 ℃～960 ℃.
Pulverizing is with corundum comminution by gas stream or corundum ball mill pulverizing.
The present invention has the following advantages compared with the prior art:
1. because of using not toxigenous organic solvent, eliminated in producing and human body to have been poisoned and the pollution of environment;
2. because of using additive, after not needing to produce the intermediate titanate earlier, be raw material production TiO with it again
2, organically form an integrated artistic flow process.Be hydrolyzed having under the additive condition, improved hydrolysis concentration, changed hydrolysising condition and TiO
2The monodispersity energy has improved work efficiency and quality product;
3. concentration time shortens dramatically, and saves the energy and raw material consumption, has reduced cost, has realized large-scale industrial production.
Figure: be technological process of production grid synoptic diagram of the present invention.
The invention will be further described below in conjunction with embodiment (accompanying drawing):
Embodiment 1:
Get TiCl
41Kg joins in the reactor that 8Kg lightweight Valelinum Liquidum is housed, in mixed solution, in batches add the 1.5Kg alcoholic acid and feed ammonia simultaneously, treat that ethanol adds after, feed ammonia in a large number, the temperature of reaction of the pressure of maintenance＜2Kg and 45 ℃ in the reactor, termination reaction when the pH value of measuring is 10.In reaction process, have volatilization gas NH
3, HCl etc. is absorbed by entering control valve and communicating pipe the encloses container that is communicated with it and solvent is housed.After reaction is finished, discharging elimination NH
4The Cl solid is inserted filtrate in another container, adds the 5g hydroxypropylcellulose and mixes, and adds the 1.2Kg high purity water again and is hydrolyzed, and stirs can stop in 20 minutes.Separate going up sectional fluid after the hydrolysis, inferior segment solution is carried out reduction vaporization except that anhydrating and ethanol liquid the TiO that obtains wetting
2Hydrate.Be made into to insert behind the powdery by lyophilize and have anti-pollution TiO
2In the electric furnace of material liner, calcining is 2.5 hours under 820 ℃ of conditions, and the discharging cooling with the development of corundum ball mill, is white high purity titanium dioxide superfine powder finished product again.With TiCl
4Meter, its productive rate is more than 38% (weight).Organic solvent and the alcohols separated recycle.
Embodiment 2:
1. get 10KgTiCl
4Join in the mixed solvent of 38Kg120 gasoline and 2Kg pyridine and become mixing solutions;
2. in mixing solutions, add 12Kg ethanol, and feed ammonia, keep reacting kettle inner pressure and be 45 ℃ of 2Kg and temperature of reaction.Ethanol in the container that volatilization gas in the still is communicated with it or petrolic solvent absorb.When pH=8, i.e. termination reaction.
3. remove NH with filtration method
4The Cl solid is squeezed into another reactor with filtrate, adds the acid of 500g polypropylene, adds the 8Kg high purity water behind the uniform mixing, stirs and finishes hydrolysis reaction in 25 minutes.
4. separate and remove upper oil phase, lower floor's colloidal sol carries out vacuum-drying and becomes powder behind ultrafiltration membrance filter under 120 ℃ of conditions.
5. with dried powder again through the calcining of 720 ℃ and 3 hours, grind with the corundum micronizer mill then, white high-purity superfine titanium dioxide powder finished product.
Claims (8)
1, a kind of manufacture method of super fine powder of titanium dioxide is with TiCL
4Be basic raw material, join and form mixed solution in the organic solvent, add alcohols again and feed ammonia that reaction generates titanic acid ester and NH
4The CL throw out, separation after removing throw out is hydrolyzed parting liquid, generates too TiO of colloidal sol
2Hydrate and organic phase, the TiO that must wet through concentrating and separating
2Hydrate carries out drying again, calcines, pulverizes, gets the superfine powder product, it is characterized in that:
1. with TiO
2Join in inertia carbon, the nitrogen organic solvent and form mixed solution, this solvent is aliphatic saturated hydrocarbon, pyridine and derivative thereof, ethers, lightweight Valelinum Liquidum, a kind of or its mixture of the gasoline of no inorganic components and naphthenic hydrocarbon, TiO
2With the weight ratio of organic solvent be 1: 2.7-18,
2. mixture is packed into can control automatically reaction pressure encloses container in, add alcohols (chemical pure) again, and feed ammonia, react alcohols add-on TiO being lower than under the reaction pressure of 16kg
24.5-6.5 times of mol, temperature of reaction is below 75 ℃, when measuring PH＞7, but termination reaction,
3. separate and remove throw out NH
4CL, adding additive amount in parting liquid is TiO
20.01-25% (weight),
4. add high purity water at normal temperatures, and reaction 3-30 minute that is hydrolyzed under constantly stirring, colloidal sol shape TiO generated
2Hydrate and upper organic phase, the adding water yield is TiCL
40.4-8 doubly (weight),
5. concentrate to remove and anhydrate and alcohol solution the TiO that must wet
2Hydrate, and carrying out drying below 180 ℃,
6. under the oxidizing atmosphere condition, adopt TiO
2The material equipment that does not produce pollution is calcined, and calcining temperature is 580 ℃-1200 ℃, and calcination time is 0.5-3 hour.
7. adopt and do not pollute TiO
2Material equipment pulverize, white high-purity superfine powder TiO
2Finished product,
2, the manufacture method of super fine powder of titanium dioxide according to claim 1, it is characterized in that: reaction is in the closed reactor of automatically controlled valve is equipped with on top, carry out under the reaction pressure 8-0.5kg, utilize the encloses container of the interior dress lyosorption that is connected with reactor by control valve simultaneously, with evaporable gas (as: NH
3, HCL, organic solvent and alcohols) sponge.
3, the manufacture method of super fine powder of titanium dioxide according to claim 1 is characterized in that alcohols is wherein a kind of or its mixed solution of ethanol, Virahol, propyl alcohol, butanols, primary isoamyl alcohol and amylalcohol.
4, the manufacture method of super fine powder of titanium dioxide according to claim 1 is characterized in that additive is that alkane hydroxylated cellulose, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose, Glacial acetic acid, polypropylene acid, polyvinyl alcohol, quadrol, polymaleic acid, nonionic surfactants OP, song draw the wherein any of ketone X-100 and trolamine and the compound material of poly-di-alcohol.
5, the manufacture method of super fine powder of titanium dioxide according to claim 1, it is characterized in that concentrating is to adopt ultrafiltration membrance filter or reduction vaporization.
6, the manufacture method of super fine powder of titanium dioxide according to claim 1 is characterized in that dry be vacuum-drying or lyophilize.
7, the manufacture method of super fine powder of titanium dioxide according to claim 1 is characterized in that calcining temperature is 720 ℃-960 ℃.
8, the manufacture method of super fine powder of titanium dioxide according to claim 1 is characterized in that pulverizing system and adopts corundum comminution by gas stream or corundum ball mill pulverizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94111732 CN1032585C (en) | 1994-04-28 | 1994-04-28 | Preparation for super fine powder of titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94111732 CN1032585C (en) | 1994-04-28 | 1994-04-28 | Preparation for super fine powder of titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1097400A CN1097400A (en) | 1995-01-18 |
| CN1032585C true CN1032585C (en) | 1996-08-21 |
Family
ID=5035570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94111732 Expired - Fee Related CN1032585C (en) | 1994-04-28 | 1994-04-28 | Preparation for super fine powder of titanium dioxide |
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| CN (1) | CN1032585C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4184487B2 (en) | 1997-08-15 | 2008-11-19 | 昭和電工株式会社 | Method for producing titanium dioxide fine particles |
| US7988947B2 (en) | 2004-11-23 | 2011-08-02 | E. I. Du Pont De Nemours And Company | Mesoporous oxide of titanium |
| US20060263291A1 (en) | 2004-11-23 | 2006-11-23 | Carmine Torardi | Mesoporous amorphous oxide of titanium |
| US7601327B2 (en) | 2004-11-23 | 2009-10-13 | E.I. Du Pont De Nemours And Company | Mesoporous oxide of hafnium |
| US7601326B2 (en) | 2004-11-23 | 2009-10-13 | E. I. Du Pont De Nemours And Company | Mesoporous oxide of zirconium |
| CN100411994C (en) * | 2006-07-07 | 2008-08-20 | 清华大学 | Process for preparing carbon-doped spherical Li4Ti5O12 |
| US7858066B2 (en) | 2007-05-08 | 2010-12-28 | E.I. Du Pont De Nemours And Company | Method of making titanium dioxide particles |
| CN104192894A (en) * | 2014-08-14 | 2014-12-10 | 仙桃市中星电子材料有限公司 | Refining method of titanium tetrachloride |
| CN105152208B (en) * | 2015-08-03 | 2017-05-03 | 华北电力大学 | Synthetic method of colorful TiO2 microsphere and application of colorful TiO2 microsphere |
| CN108751252B (en) * | 2018-06-07 | 2020-05-19 | 广西藤县广峰钛白有限公司 | Preparation method of titanium dioxide with controllable particle size |
| CN109456169B (en) * | 2018-11-21 | 2021-03-23 | 常州大学 | Synthesis of high-content fatty acid monoglyceride and co-production of nano TiO2Method (2) |
| CN112239224A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Method for recovering titanium tetrachloride |
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1994
- 1994-04-28 CN CN 94111732 patent/CN1032585C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1097400A (en) | 1995-01-18 |
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Granted publication date: 19960821 |