CN1752016A - A kind of novel nano-titanium dioxide powder preparation method - Google Patents
A kind of novel nano-titanium dioxide powder preparation method Download PDFInfo
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Abstract
The invention belongs to chemical technology field, be specifically related to a kind of novel nano-titanium dioxide powder preparation method.The method that solid-solid phase that the present invention adopts transforms joins the hydrochloric acid soln in the titanium source of respective amount in the aqueous solution of an amount of alkaline matter, and hierarchy of control pH is 7～8, this moment adularescent Ti (OH)
4Precipitation generates, and precipitation adds an amount of organic acid after washing after filtration, and thorough mixing obtains precursor.Precursor is calcined 0.5～1.5h under 550-650 ℃ of condition in air, obtain the nano titanium oxide of anatase titanium dioxide, particle diameter is 15～20nm; If precursor is calcined 0.5～2.5h under 750-850 ℃ of condition, then obtain rutile type nano titanic oxide, particle diameter is 20～25nm.The nano titanium oxide that makes can be widely used in fields such as the cosmetics of super quality, coating, plastics.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of novel nano-titanium dioxide powder preparation method.
Background technology
Nano titanium oxide is a kind of very important industrial chemicals, is divided into anatase titanium dioxide, rutile-type and three kinds of crystal formations of plate titanium type.Nanometer anatase titania is as a kind of novel photocatalysis agent, anti UV agent and photovoltaic effect agent, at antimycotic antiseptic, purify air, deodorization, water treatment, aspect such as antifouling demonstrate wide application prospect.Advantages such as rutile type nano titanic oxide has specific refractory power height, good weatherability, photochemical activity is little, opacifying power is big, physical and chemical performance is stable, be the indispensable raw materials in field such as electronics, light industry, chemical industry, be widely used in fields such as plastics, enamel, artificial fiber, electronic material, rubber, coating.
At present, the preparation method of relevant nano titanium oxide mainly contains: hydrothermal synthesis method, control hydrolysis method, sol-gel method, microemulsion method, the precipitator method, chemical Vapor deposition process etc.Hydrothermal synthesis method, the advantage of this method are that the product crystallization degree is good, and deficiency is that reaction conditions is high temperature, high pressure, thereby aspects such as equipment material, safety are required harsh.The control hydrolysis method makes titanium salt hydrolysis under the condition of strictness control by regulating the hydrolysis rate of titanium salt, can make nano-titanium dioxide powder.The advantage of this method is simple to operate, and cost is cheap relatively, easily takes place in washing and filtering and the drying process to run off and agglomeration but exist, and causes nano-TiO
2Yield and particle diameter all be affected.Sol-gel method is to be raw material with the titanium alkoxide, is hydrolyzed in organic medium, polycondensation, makes solution behind colloidal sol, gelation process, and gel drying is sintered into the method for powder.The nano titanium dioxide powder particle diameter of this method preparation is little, is evenly distributed good dispersity, but owing to will be raw material with the titanium alkoxide, add a large amount of organic reagents again, cost is higher, owing to the generation of gel, organic reagent is difficult for overflowing simultaneously, and dry, sintering process easily produces Prevent Carbon Contamination.Microemulsion method though the structure of microemulsion has fundamentally limited the particulate growth, makes the preparation of ultrafine powder become easy.But this method only is suitable for laboratory study, is not suitable for suitability for industrialized production.At present, main employing is the control hydrolysis method and the precipitator method in the production, the advantage of these two class methods is production efficiency height, cost is low, pollution is little, deficiency is that these two class methods will directly be calcined with the precursor that alkali precipitation or hydrolytic precipitation obtain, there are deficiencies such as particle diameter is inhomogeneous, product is easily reunited, purity is low, limited the performance of the many excellent properties of product.
Summary of the invention
The objective of the invention is to propose a kind of reducing production costs, solve the novel nano-titanium dioxide powder preparation method of traditional agglomeration traits.
The novel nano-titanium dioxide powder preparation method that the present invention proposes, the method that adopts solid-solid phase to transform makes the titanium dioxide powder material, and its concrete steps are: the titanium source is joined in the hydrochloric acid soln, obtain the hydrochloric acid soln in titanium source; Hydrochloric acid soln with the titanium source joins in the aqueous solution of alkaline matter then, and the pH of the hierarchy of control is 7～8, generates the Ti (OH) of white
4Precipitation is filtered, and cleans, and obtains precipitated product Ti (OH)
4Again to precipitated product Ti (OH)
4In add organic acid, thorough mixing makes the oxyhydroxide of titanium be converted into the organic salt of titanium, obtains precursor; The precursor that obtains is put into crucible place the retort furnace calcination, obtain thick finished product; Again thick finished product is pulverized, obtained required product.
Actual conditions is:
The volumetric molar concentration of the hydrochloric acid soln that dissolving titanium source is used is 2～4mol/L;
The hydrochloric acid soln volumetric molar concentration in titanium source is 0.1～8mol/L;
Alkaline matter can adopt a kind of of ammoniacal liquor, yellow soda ash, sodium hydroxide, potassium hydroxide etc., and when alkaline matter was ammoniacal liquor, the volume ratio in ammoniacal liquor and titanium source was 0.8: 1～1.4: 1; When alkaline matter was yellow soda ash, the mass ratio in yellow soda ash and titanium source was 0.8: 1～1.2: 1; When alkaline matter was sodium hydroxide or potassium hydroxide, the mass ratio in sodium hydroxide or potassium hydroxide and titanium source was: 1: 0.2～1: 0.6;
The mass ratio in organic acid and titanium source is 0.8: 1～1.4: 1;
Calcination: precursor was calcined 0.5～1.5 hour under 550～650 ℃ of conditions, obtained the nano titanium oxide of anatase titanium dioxide; Under 750～850 ℃ of conditions, calcined 0.5～2.5 hour, obtain the nano titanium oxide of rutile-type;
Above-mentioned titanium source is a kind of of titanium tetrachloride, titanium sulfate.
Among the present invention, described organic acid can be a kind of of formic acid, acetate, tartrate, citric acid, Whitfield's ointment etc.
Among the present invention, pulverizing can be adopted ball mill or micronizer mill.
The present invention's implementation condition preferably is:
Alkaline matter is a kind of of ammoniacal liquor, yellow soda ash.
The volume ratio in ammoniacal liquor and titanium source is 0.9: 1～1.1: 1.
The mass ratio in yellow soda ash and titanium source is 0.9: 1～1.1: 1.
The mass ratio in sodium hydroxide or potassium hydroxide and titanium source is: 1: 0.3～1: 0.5.
The mass ratio in organic acid and titanium source is 0.9: 1～1.1: 1.
Among the present invention, cleaning is in order effectively to remove foreign ion, as chlorion, ammonium ion or sodium ion etc.
Among the present invention, because the precursor of gained is organic acid salt (as the formate of titanium, a tartrate etc.), organic acid salt can produce a large amount of pollution-free gases in decomposition course, as gases such as carbonic acid gas, water vapors, make reaction system loose, prevented the generation of agglomeration effectively.
The product of the present invention through obtaining after calcining detects through transmission electron microscope, and the particle diameter of anatase titanium dioxide product is 15～20nm, and the particle diameter of rutile titanium dioxide product is 20～25nm.
The present invention has following advantage:
1, proposes first in the product that alkali precipitation obtains, to add organic acid, the organic acid salt that the oxyhydroxide of titanium is converted into titanium is prepared target product as precursor by solid-solid reaction.Because precursor is an organic salt, has produced a large amount of nonstaining property gases in decomposition course, make reaction system loose, effectively prevented the generation of agglomeration.
2, the used starting material of the present invention source is sufficient and cheap, and energy consumption is little in the production process, low production cost.
3, the product that utilizes the present invention to prepare is compared with like product, has the purity height, and whiteness is good, the little and homogeneous of particle diameter, and no agglomeration is easy to characteristics such as dispersion.
Embodiment
The present invention is further illustrated below by specific embodiment.
Embodiment 1:
Get 50ml, volumetric molar concentration is 0.1mol/L titanium tetrachloride hydrochloric acid (volumetric molar concentration is a 2mol/L) solution, join in the 400ml aqueous solution that contains 25ml ammoniacal liquor, this moment adularescent Ti (OH)
4Precipitation generates, and filters, and water cleans 2～3 times, till existing with the no chlorion of Silver Nitrate detection to washing lotion, obtains precipitated product.Add citric acid 1g in the precipitated product that obtains, thorough mixing obtains precursor.Precursor is put into porcelain crucible be placed on retort furnace, slowly be warming up to 600 ℃, calcining 1h obtains crude product.This crude product obtains nano-titanium dioxide powder 0.4g after pulverizing through ball mill pulverizer.X ray powder diffraction instrument (XRD) analytical results shows that this product is the anatase crystal structure; By tem study, the particle diameter of product is 17nm.If precursor ball mill pulverizing behind calcining 0.5h under 850 ℃ of conditions then obtains rutile type nano titanic oxide 0.4g, by tem study, the particle diameter of product is 22nm.
Embodiment 2:
Get 50ml, volumetric molar concentration is hydrochloric acid (volumetric molar concentration the is 3mol/L) solution of 5mol/L titanium sulfate, join in the 400ml water that contains 20g sodium hydroxide, this moment adularescent Ti (OH)
4Precipitation generates, and filters, and water cleans 2～3 times, till existing with the no chlorion of bariumchloride detection to washing lotion, obtains precipitated product.Add formic acid 55ml in the precipitated product that obtains, thorough mixing obtains precursor.Precursor is put into porcelain crucible be placed on retort furnace, slowly be warming up to 650 ℃, calcining 0.5h obtains the nano titanium oxide crude product.This crude product obtains nano-titanium dioxide powder 19g through comminution by gas stream.Analyze by x ray powder diffraction instrument (XRD), this product is a nanometer anatase titania; By tem study, the particle diameter of product is 20nm.If precursor is comminution by gas stream behind calcining 1.5h under 800 ℃ of conditions, then obtain rutile type nano titanic oxide, by tem study, the particle diameter of product is 25nm.
Embodiment 3:
Get 50ml, volumetric molar concentration is hydrochloric acid (volumetric molar concentration the is 4mol/L) solution of 5mol/L titanium tetrachloride, join in the 400ml water that contains 50g yellow soda ash, this moment adularescent Ti (OH)
4Precipitation generates, and filters, and water cleans 2-3 time, till existing with the no chlorion of Silver Nitrate detection to washing lotion, obtains precipitated product.Add Whitfield's ointment 27g in the precipitated product that obtains, thorough mixing obtains precursor, and precursor is placed porcelain crucible, again porcelain crucible is put into retort furnace, slowly is warming up to 600 ℃, and calcining 1h obtains the nano titanium oxide crude product.Crude product obtains end product 10g behind comminution by gas stream.Analyze by x ray powder diffraction instrument (XRD), this product is a nanometer anatase titania; By tem study, the particle diameter of product is 20nm.If precursor is comminution by gas stream behind calcining 2.5h under 750 ℃ of conditions, then obtain rutile type nano titanic oxide 10g, by tem study, the particle diameter of product is 25nm.
Embodiment 4:
Get 50ml, volumetric molar concentration is hydrochloric acid (volumetric molar concentration the is 4mol/L) solution of 5mol/L titanium tetrachloride, join in the 400ml water that contains 50g yellow soda ash, this moment adularescent Ti (OH)
4Precipitation generates, and filters, and water cleans 2-3 time, till existing with the no chlorion of Silver Nitrate detection to washing lotion, obtains precipitated product.Add acetate 55ml in the precipitated product that obtains, thorough mixing obtains precursor.Precursor is put into behind the crucible as for retort furnace, slowly be warming up to 650 ℃, calcining 0.5h obtains the nano titanium oxide crude product, pulverizes through micronizer mill, obtains final product 21g.Analyze by x ray powder diffraction instrument (XRD), this product is a nanometer anatase titania; By tem study, the particle diameter of product is 19nm.If precursor is comminution by gas stream again behind calcining 1h under 800 ℃ of conditions, then obtain rutile type nano titanic oxide, by tem study, the particle diameter of product is 24nm.
Embodiment 5:
Get 50ml, volumetric molar concentration is hydrochloric acid (volumetric molar concentration the is 4mol/L) solution of 8mol/L titanium tetrachloride, join in the 400ml aqueous solution that contains 100ml ammoniacal liquor, this moment adularescent Ti (OH)
4Precipitation generates, and filters, and water cleans 2-3 time, obtains precipitated product.Add tartrate 80g in the precipitated product that obtains, thorough mixing obtains precursor.Precursor is put into crucible be placed on retort furnace, slowly be warming up to 550 ℃, calcining 1.5h gets crude product.This crude product obtains nano-titanium dioxide powder 32g behind comminution by gas stream.Analyze by x ray powder diffraction instrument (XRD), this powder is an anatase titanium dioxide; By tem study, the particle diameter of product is 18nm.Slowly be warming up to 850 ℃ as precursor, calcining 0.5h, the crude product that obtains then obtains rutile type nano titanic oxide behind comminution by gas stream, and by tem study, the particle diameter of product is 40nm.
Claims (8)
1, a kind of novel nano titanium oxide preparation method, the method that it is characterized in that adopting solid-solid phase to transform, concrete steps are: will join in the hydrochloric acid soln as the starting material in titanium source, and obtain the hydrochloric acid soln in titanium source; Hydrochloric acid soln with the titanium source joins in the aqueous solution of alkaline matter then, and the pH of the hierarchy of control is 7～8, generates the Ti (OH) of white
4Precipitation is filtered, and cleans, and obtains precipitated product Ti (OH)
4Again to precipitated product Ti (OH)
4In add organic acid, thorough mixing makes the oxyhydroxide of titanium be converted into the organic salt of titanium, obtains precursor; The precursor that obtains is put into crucible place the retort furnace calcination, obtain thick finished product; Again thick finished product is pulverized, obtained required product;
Actual conditions is:
The volumetric molar concentration of the hydrochloric acid soln that dissolving titanium source is used is 2～4mol/L;
The hydrochloric acid soln volumetric molar concentration in titanium source is 0.1～8mol/L;
Alkaline matter can adopt a kind of of ammoniacal liquor, yellow soda ash, sodium hydroxide, potassium hydroxide, and when alkaline matter was ammoniacal liquor, the volume ratio in ammoniacal liquor and titanium source was 0.8: 1～1.4: 1; When alkaline matter was yellow soda ash, the mass ratio in yellow soda ash and titanium source was 0.8: 1～1.2: 1; When alkaline matter was sodium hydroxide or potassium hydroxide, the mass ratio in sodium hydroxide or potassium hydroxide and titanium source was: 1: 0.2～1: 0.6;
The mass ratio in organic acid and titanium source is 0.8: 1～1.4: 1;
Calcination: precursor was calcined 0.5～1.5 hour under 550～650 ℃ of conditions, obtained the nano titanium oxide of anatase titanium dioxide; Under 750～850 ℃ of conditions, calcined 0.5～2.5 hour, obtain the nano titanium oxide of rutile-type;
Above-mentioned titanium source is a kind of of titanium tetrachloride, titanium sulfate.
2, novel nano titanium oxide preparation method according to claim 1 is characterized in that described organic acid is a kind of of formic acid, acetate, tartrate, citric acid, Whitfield's ointment.
3, novel nano titanium oxide preparation method according to claim 1 is characterized in that pulverizing employing ball mill or micronizer mill.
4, novel nano titanium oxide preparation method according to claim 1 is characterized in that alkaline matter is a kind of of ammoniacal liquor, yellow soda ash.
5, novel nano titanium oxide preparation method according to claim 1, the volume ratio that it is characterized in that ammoniacal liquor and titanium source is 0.9: 1～1.1: 1.
6, novel nano titanium oxide preparation method according to claim 1, the mass ratio that it is characterized in that yellow soda ash and titanium source is 0.9: 1～1.1: 1.
7, novel nano titanium oxide preparation method according to claim 1 is characterized in that the mass ratio in sodium hydroxide or potassium hydroxide and titanium source is: 1: 0.3～1: 0.5.
8, novel nano titanium oxide preparation method according to claim 1, the mass ratio that it is characterized in that organic acid and titanium source is 0.9: 1～1.1: 1.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100453466C (en) * | 2006-12-20 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | Synthesis method of non-aqueous nanometer anatase titania |
| CN101654280B (en) * | 2009-08-25 | 2011-04-13 | 苏州大学 | Preparation method of titanium dioxide nano powder |
| CN102600880A (en) * | 2012-01-29 | 2012-07-25 | 北京科技大学 | Preparation method of visible light-response titanium dioxide photocatalytic liquid |
| CN102107907B (en) * | 2009-12-28 | 2012-11-28 | 中国科学院金属研究所 | Porous nano hydrated titanium dioxide dearsenifying material and preparation method thereof |
| CN103754930A (en) * | 2014-01-07 | 2014-04-30 | 福建师范大学 | Octahedron anatase TiO2 orderly superstructure as well as preparation and application thereof |
| CN108516584A (en) * | 2018-07-09 | 2018-09-11 | 江苏中研创星材料科技有限公司 | A kind of preparation method of high-purity super large specific surface poriferous titanium dioxide |
| CN110943171A (en) * | 2018-09-21 | 2020-03-31 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| WO2021028769A1 (en) * | 2019-08-13 | 2021-02-18 | Vice Chancellor, Sabaragamuwa University Of Sri Lanka | Process and system for extarcting titanium dioxide nanomaterials from natural ilmenite |
| CN114105194A (en) * | 2021-12-24 | 2022-03-01 | 济南裕兴化工有限责任公司 | Method for promoting crystal form transformation of titanium white |
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| US6375923B1 (en) * | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
| US6440383B1 (en) * | 1999-06-24 | 2002-08-27 | Altair Nanomaterials Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
| CN1363521A (en) * | 2001-01-09 | 2002-08-14 | 攀枝花市永禄科技开发有限责任公司 | Process for preparing anatase crystal type nano TiO2 |
| CN1363520A (en) * | 2001-01-09 | 2002-08-14 | 攀枝花市永禄科技开发有限责任公司 | Process for preparing rutile crystal type nano TiO2 |
| CN1506311A (en) * | 2002-12-09 | 2004-06-23 | 攀枝花钢铁有限责任公司钢铁研究院 | Prepn process of nano level rutile-type titania powder |
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- 2005-07-28 CN CNB2005100282507A patent/CN100445209C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100453466C (en) * | 2006-12-20 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | Synthesis method of non-aqueous nanometer anatase titania |
| CN101654280B (en) * | 2009-08-25 | 2011-04-13 | 苏州大学 | Preparation method of titanium dioxide nano powder |
| CN102107907B (en) * | 2009-12-28 | 2012-11-28 | 中国科学院金属研究所 | Porous nano hydrated titanium dioxide dearsenifying material and preparation method thereof |
| CN102600880A (en) * | 2012-01-29 | 2012-07-25 | 北京科技大学 | Preparation method of visible light-response titanium dioxide photocatalytic liquid |
| CN103754930A (en) * | 2014-01-07 | 2014-04-30 | 福建师范大学 | Octahedron anatase TiO2 orderly superstructure as well as preparation and application thereof |
| CN103754930B (en) * | 2014-01-07 | 2015-07-22 | 福建师范大学 | Octahedron anatase TiO2 orderly superstructure as well as preparation and application thereof |
| CN108516584A (en) * | 2018-07-09 | 2018-09-11 | 江苏中研创星材料科技有限公司 | A kind of preparation method of high-purity super large specific surface poriferous titanium dioxide |
| CN108516584B (en) * | 2018-07-09 | 2020-05-08 | 江苏中研创星材料科技有限公司 | Preparation method of high-purity super-large specific surface porous titanium dioxide |
| CN110943171A (en) * | 2018-09-21 | 2020-03-31 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| WO2021028769A1 (en) * | 2019-08-13 | 2021-02-18 | Vice Chancellor, Sabaragamuwa University Of Sri Lanka | Process and system for extarcting titanium dioxide nanomaterials from natural ilmenite |
| CN114105194A (en) * | 2021-12-24 | 2022-03-01 | 济南裕兴化工有限责任公司 | Method for promoting crystal form transformation of titanium white |
| CN114105194B (en) * | 2021-12-24 | 2023-10-24 | 济南裕兴化工有限责任公司 | Method for promoting titanium white crystal form conversion |
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