CN1206164C - Method for preparing liquid state predecessor of nano titanium dioxide - Google Patents
Method for preparing liquid state predecessor of nano titanium dioxide Download PDFInfo
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- CN1206164C CN1206164C CN 03117289 CN03117289A CN1206164C CN 1206164 C CN1206164 C CN 1206164C CN 03117289 CN03117289 CN 03117289 CN 03117289 A CN03117289 A CN 03117289A CN 1206164 C CN1206164 C CN 1206164C
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Abstract
The present invention relates to a method for preparing a liquid predecessor of nano titanium dioxides, which is characterized in that preparation is carried out according to the following steps: (1), a compound containing titanium is treated into orthotitanate; (2), pure water is used for washing the obtained orthotitanate, and orthotitanate deposition is obtained; (3), an organic complex which can form a water-soluble complex compound with titanium ions is added into the orthotitanate deposition, the pure water is added, and the quantity of the added water is from 0.1 to 5 times of the weight of TiO2 contained in the orthotitanate deposition. Through stir, the added organic complex and the orthotitanate deposition sufficiently react, and an organic complex compound of titanium is obtained, namely the liquid predecessor of nano titanium dioxides. The method can prepare the liquid predecessor of nano titanium dioxides, the main component of the liquid predecessor of nano titanium dioxides are the organic complex compound of titanium, and the organic complex compound of titanium can obtain nano titanium dioxide powder by heat decomposition like foreign 'slurry titanium white'.
Description
Technical field
The present invention relates to a kind of preparation method of nano titanium oxide, especially a kind of preparation method of nano titanium oxide liquid precursor.
Background technology
Nano titanium oxide has many special functions, for example: nm volume effect, Nanosurface effect, quantum size effect, macro quanta tunnel effect etc. have important application prospects at aspects such as preparation photoelectrochemical cell, plasma device, ferroelectric material, photosensor, gas sensor, photodissociation hydrophone spare, antifog glass, organism Photodegradation catalysts.
The Chinese invention patent application discloses a kind of method for preparing nanometre-grade titanic-schorl type titanium dioxide for No. 97120161.7, and this method is a raw material with titanium sulfate, titanyl sulfate or metatitanic acid, is precipitation agent with yellow soda ash, and zinc sulfate is for disperseing transforming agent; Use yellow soda ash hydrolysis titanium sulfate etc. earlier, the zinc subcarbonate that forms with the zinc sulfate carbonization coats the positive metatitanic acid that hydrolysis produces again, after this positive metatitanic acid carried out pre-calcination, dissolve away zinc oxide with sulfuric acid, the metatitanic acid that obtains after acid is molten is delivered to the crystal formation converter, at high temperature carry out crystal formation and transform, obtain the nano-titanium dioxide powder product.In No. 97108439.4, Chinese invention patent application, the another kind of method for preparing Nano titanium dioxide is then disclosed, the key problem in technology of this method is: be raw material with the metatitanic acid, urea is the precipitation from homogeneous solution agent, obtains precipitating TiO (OH) after the reaction
2, to after this throw out calcining, promptly get Nano titanium dioxide again.In No. 96117100.6, Chinese invention patent application, a kind of manufacture method of nano titanium oxide is also disclosed, it is main raw material that this method is selected wet metatitanic acid for use, adds volatile salt, makes the SO of chemisorption
3Desorption and neutralization are acid, repeatedly wash and remove SO
4 2-, obtain the wet metatitanic acid of purifying, after this add the polymeric surface active agent making beating again, with polymeric surface active agent as dispersion agent, behind dispersion and emulsion, technologies such as drying, thermal treatment, pulverizing are prepared nano rutile-type and nano-anatase mine-titanium oxide powder again.In addition, abroad also adopted several different methods such as titanium alkoxide process to carry out the preparation research of nano-titanium dioxide powder, and realized suitability for industrialized production.But above-mentioned multiple preparation method's product is powder type nano titanium oxide.Make powder type nano titanium oxide in substrate, form relatively difficulty of film; And nano-powder is extremely unstable, easily self reunite or the absorption environment in moisture, gaseous substance and solid dust, thereby its storage time is shorter, this makes the application of nano-titanium dioxide powder have significant limitation, external for this reason scientific and technical personnel study " slurry type titanium white " and have obtained some progress, in China, the research of " slurry type titanium white " still is in the blank stage.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the nano titanium oxide liquid precursor.
Preparation method of the present invention carries out according to the following steps: (1), titanium-containing compound is treated to positive titanate; (2), the positive titanate of gained is repeatedly washed, obtain the titanic Acid precipitation with pure water; (3), can add in the titanic Acid precipitation with the organic complexing agent that titanium ion forms water soluble complex and add pure water, institute's amount of water is contained TiO in the titanic Acid precipitation
20.1～5 times of weight fully reacts the organic complexing agent and the titanic Acid precipitation that are added through stirring, obtains the organic complex of titanium, i.e. the nano titanium oxide liquid precursor.
In step of the present invention (1), the approach that titanium-containing compound is treated to positive titanate is a lot, can directly adopt prior art to finish.Titanium-containing compound as main raw material can be anatase titanium dioxide or metatitanic acid, also can be titanium sulfate (titanyl sulfate).When with anatase titanium dioxide or metatitanic acid during as main raw material, can adopt alkali fusion that it is handled and obtain positive titanate, concrete steps are (following consumption is weight part): get 1 part of anatase titanium dioxide, 2～5 parts in caustic soda, or get and contain 1 part of TiO
22～5 parts in metatitanic acid (measuring and metering), caustic soda with mud scale, carried out fusion 1～3 hour with iron ware, just can obtain positive titanate (just sodium titanate).Simultaneously, when with anatase titanium dioxide or metatitanic acid during as main raw material, can also adopt sulfuric acid process that it is handled and obtain positive titanate, concrete steps are (following consumption is weight part): get 1 part of anatase titanium dioxide, 2～5 parts in sulfuric acid (in 100%), or get and contain 1 part of TiO
2Metatitanic acid (measuring and metering) with mud scale, add sulfuric acid (in 100%) 1～3 part, wherein make vitriolic concentration be formulated as 55%～65%, 130～140 ℃ of reactions 12～16 hours, obtain titanium sulfate (titanyl sulfate) solution; Adding ammoniacal liquor or caustic soda carry out neutralization reaction in resulting titanium sulfate (titanyl sulfate) solution again, make pH value reach 2.5～3.5, finally obtain positive titanium acid ammonium or positive sodium titanate precipitation.When with titanium sulfate (titanyl sulfate) during as main raw material, then can directly adopt following method that titanium sulfate (titanyl sulfate) is handled and obtain positive titanate: in titanium sulfate (titanyl sulfate) solution, add ammoniacal liquor or caustic soda carries out neutralization reaction, make pH value reach 2.5～3.5, finally obtain positive titanium acid ammonium or positive sodium titanate precipitation.
Step of the present invention (2) also can directly utilize prior art to finish, and promptly uses pure water (deionized water or distilled water) that the positive titanate of gained is washed, and obtains the titanic Acid precipitation.During concrete operations, can will contain 100 parts of TiO with pure water
2Positive titanate (measuring and metering) with mud scale wash, make it be converted into positive metatitanic acid, and make sodium ion or ammonium ion content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 0.5～1.5 with hydrochloric acid, adds 0.5～5 part of (weight part) zinc powder, under stirring zinc powder is reacted completely, and regulates pH value to 2.5～3.5 with ammoniacal liquor, washs with pure water again, makes iron ion content be lower than 10
-5% finally obtains pure titanic Acid precipitation.Here, the purpose that adds zinc powder is in order to make ferric ion be reduced to ferrous ion, to remove so that iron ion thoroughly can be washed in the scope of pH value 2.5～3.5.
Creative contribution of the present invention mainly is step (3), promptly is can add with the organic complexing agent that titanium ion forms water soluble complex in the titanic Acid precipitation and add pure water (institute's amount of water can be contained TiO in the titanic Acid precipitation in right amount
20.1～5 times of weight, can determine according to the purposes of finished product), make the organic complexing agent and the titanic Acid precipitation that are added fully react (also can suitably be heated to below 100 ℃) through stirring, obtain the organic complex of titanium, and with the organic complex of this titanium as the titanium dioxide liquid precursor.In the present invention, said pure water can be deionized water or distilled water.In the prior art, can have multiple with the organic complexing agent that titanium ion forms water soluble complex, as oxalic acid, tartrate, EDTA (ethylenediamine tetraacetic acid (EDTA)) etc., they can form titanium oxyoxalate complex compound, tartrate oxygen titanium complex and EDTA oxygen titanium complex with titanium ion respectively.The add-on of organic complexing agent is looked the composition of the complexing agent that adopts and is determined that for example, for oxalic acid, its add-on is TiO in the positive metatitanic acid
20.5～4 times (weight ratio) of content, for tartrate, its add-on then is TiO in the positive metatitanic acid
20.85～7 times (weight ratio) of content.Because oxalic acid is cheap, can reduce production costs as organic complexing agent with it.Experimental result shows: after above-mentioned titanium dioxide liquid precursor is dried, 700～820 ℃ of thermolysiss of carrying out about 1 hour, can obtain the rutile titanium dioxide powder of 10～35 nanometers.
In traditional method, the preparation rutile titanium dioxide need be introduced salt acid-sol crystal seed TiOCl
2As inducing transforming agent, and [TiO (the C in the titanium oxyoxalate complex compound
2O
4)
2]
2-, [TiO (C
2O
4)] and tartrate oxygen titanium complex and EDTA oxygen titanium complex etc. itself possessed and had and crystal seed TiOCl
2Similar character is so carry out the pyrolysated product just in time based on rutile titanium dioxide at 700～820 ℃; When this titanium dioxide precursor was decomposing, the major part of its composition vapored away with gas form, and the organic complexing agent of cocrystallization has buffer action, thereby can make degradation production TiO
2Granularity is a nano level.
With the titanium oxyoxalate complex compound is example, and its pyrolysis equation is as follows:
With tartrate oxygen titanium complex is example, and its pyrolysis equation is as follows:
Therefore, compare with aforementioned existing method, method of the present invention can be prepared the nano titanium oxide liquid precursor.The main component of this nano titanium oxide liquid precursor is the organic complex of titanium, it is the same with external " slurry type titanium white " to have following advantage: can obtain nano-titanium dioxide powder by thermolysis, can on material substrate such as pottery, glass and metal, form the precursor film, obtain corresponding nano-titanium dioxide film through thermolysis, can overcome short shortcoming of nano-titanium dioxide powder storage time.Simultaneously, present method has substituted the alkoxide cpd of employed titanium in the traditional method with the organic complex of titanium, makes the preparation method more simple, and cost reduces greatly, constant product quality, and the purity height, product is easy to use, is easy to suitability for industrialized production.
Content of the present invention further illustrates with the following Examples, but content of the present invention is not limited only to content related among the embodiment.
Description of drawings
Fig. 1 is the X-ray diffractogram of the nano titanium oxide that makes with made titanium dioxide liquid precursor among the embodiment 1.
Fig. 2 is the transmission electron microscope photo scanning figure of the nano titanium oxide that makes with made titanium dioxide liquid precursor among the embodiment 1.
Embodiment
Embodiment 1: choose anatase titanium dioxide 100 grams and be main raw material, add caustic soda 250 grams, carried out fusion 2 hours with iron ware, obtain the positive sodium titanate solid of vesicular.With the positive sodium titanate of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 0.8 with hydrochloric acid, adds 1.5 gram zinc powders, stirs zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains pure titanic sour water and closes precipitation.At last 150 gram oxalic acid (purity is in 100%) are added in the pure titanic Acid precipitation, add 20 ml pure waters, in container, stir, finally obtain the nano titanium oxide liquid precursor.
Main chemical reactions formula among the embodiment 1 has:
The nano titanium oxide liquid precursor that obtains with present embodiment is carried out (the cracking chemical reaction formula is seen before and stated) after the thermolysis, and every Measurement results of the nano titanium oxide that makes is as follows:
1., crystal formation: the X-ray diffraction analysis, the powder that obtains is a rutile TiO
2, each diffraction peak is in strict conformity with rutile TiO
2The standard card value, X-ray diffraction analysis chart and data are seen accompanying drawing 1.
2., chemical composition analysis: chemical composition analysis data such as following table 1.
The TiO of this prepared of table 1
2The main component index
| Weight (TiO 2)％ | Weight (Na 2O)％ | Weight (K 2O)％ | Weight (CaO) % | Weight (Fe 2O 3)％ |
| 99.97 | 0.001 | 0.002 | 0.002 | 0.001 |
3., granularity: with the transmission electron microscope test, the powder granularity that is obtained is 10～35nm scope, for spherical powder is seen accompanying drawing 2.
Embodiment 2: present embodiment is similar to embodiment 1.In the present embodiment, choose anatase titanium dioxide 100 grams and be main raw material, add caustic soda 400 grams, carried out fusion 2 hours, obtain the positive sodium titanate solid of vesicular with iron ware.With the positive sodium titanate of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 3.5 gram zinc powders, stirs zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains pure titanic sour water and closes precipitation.350 gram oxalic acid (purity is in 100%) are added in the pure titanic Acid precipitation, add 400 ml distilled waters, in container, stir, finally obtain the nano titanium oxide liquid precursor.
Embodiment 3: choose metatitanic acid 310 grams and (measure TiO in the actual metatitanic acid with mud scale
2Content, in this example 310 the gram metatitanic acids be equivalent to contain 100 the gram TiO
2) be main raw material, add caustic soda 230 grams, carried out fusion 2 hours with iron ware, obtain the positive sodium titanate solid of vesicular.With deionized water wash titanic acid sodium, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 0.8 with hydrochloric acid, adds 1.6 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with deionized water again, makes iron ion content be lower than 10
-5% obtains pure titanic Acid precipitation.130 gram oxalic acid (purity is in 100%) are added in the pure titanic Acid precipitation, add 20 ml pure waters, in container, stir, finally obtain the nano titanium oxide liquid precursor.
Main chemical reactions formula among the embodiment 3 has:
Other chemical equation is with aforementioned reaction formula (2), (3) and (4).
Embodiment 4: present embodiment is similar to embodiment 3.In the present embodiment, choose metatitanic acid 310 grams and (measure TiO in the actual metatitanic acid with mud scale
2Content, in this example 310 the gram metatitanic acids be equivalent to contain 100 the gram TiO
2) be main raw material, add caustic soda 430 grams, carried out fusion 2 hours with iron ware, obtain the positive sodium titanate solid of vesicular.With the positive sodium titanate of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 3.6 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains pure titanic Acid precipitation.230 gram oxalic acid (purity is in 100%) are added in the pure titanic Acid precipitation, add 40 ml pure waters, in container, stir, finally obtain the nano titanium oxide liquid precursor.
Embodiment 5: get anatase titanium dioxide 100 gram, add sulfuric acid (in 100%) 230 grams, it is 60% solution that sulfuric acid is formulated as concentration, 125 ℃ of reactions 14 hours, obtains titanium sulfate (titanyl sulfate) solution.Titanium sulfate (titanyl sulfate) solution is added ammoniacal liquor carry out neutralization reaction, make pH value reach 2.5, obtain positive titanium acid ammonium.With the positive titanium acid ammonium of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 2.0 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains pure titanic Acid precipitation.100 gram oxalic acid (purity is in 100%) are added in the pure titanic Acid precipitation, add 10 ml distilled waters, in container, stir, obtain the nano titanium oxide liquid precursor.
Main chemical reactions formula among the embodiment 5 has:
The chemical equation of positive metatitanic acid and oxalic acid sees before and states reaction formula (4).
Embodiment 6: present embodiment is similar to embodiment 5.In the present embodiment, get anatase titanium dioxide 100 gram, add sulfuric acid (in 100%) 460 grams, it is 60% solution that sulfuric acid is formulated as concentration, 135 ℃ of reactions 15 hours, obtains titanium sulfate (titanyl sulfate) solution.Titanium sulfate (titanyl sulfate) solution is added caustic soda (in advance caustic soda is mixed with weight percent concentration be 10% solution) carry out neutralization reaction, make pH value reach 2.5, obtain positive sodium titanate.With the positive sodium titanate of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 1.5 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains pure titanic Acid precipitation.300 gram oxalic acid (purity is in 100%) are added in the pure titanic Acid precipitation, add 145 ml distilled waters, in container, stir, obtain the nano titanium oxide liquid precursor.
In the present embodiment, the chemical equation of titanium sulfate (titanyl sulfate) solution and caustic soda is:
Embodiment 7: choose metatitanic acid 310 grams and (measure TiO in the actual metatitanic acid with mud scale
2Content, in this example 310 the gram metatitanic acids be equivalent to contain 100 the gram TiO
2) be main raw material, add sulfuric acid (in 100%) 130 grams, it is 60% solution that sulfuric acid is formulated as concentration, 125 ℃ of reactions 14 hours, obtains titanium sulfate (titanyl sulfate) solution.In titanium sulfate (titanyl sulfate) solution, add ammoniacal liquor and carry out neutralization reaction, make pH value reach 2.5, obtain positive titanium acid ammonium.With the positive titanium acid ammonium of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 1.0 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains pure titanic Acid precipitation.100 gram oxalic acid (purity is in 100%) are added in the pure titanic Acid precipitation, add 15 ml distilled waters, in container, stir, obtain the nano titanium oxide liquid precursor.
Main chemical reactions formula among the embodiment 7 has:
The chemical equation of positive metatitanic acid and oxalic acid sees before and states reaction formula (4).
Embodiment 8: present embodiment is similar to embodiment 7.In the present embodiment, choose metatitanic acid 310 grams and (measure TiO in the actual metatitanic acid with mud scale
2Content, in this example 310 the gram metatitanic acids be equivalent to contain 100 the gram TiO
2) be main raw material, add sulfuric acid (in 100%) 260 grams, it is 60% solution that sulfuric acid is formulated as concentration, 135 ℃ of reactions 15 hours, obtains titanium sulfate (titanyl sulfate) solution.In titanium sulfate (titanyl sulfate) solution, add caustic soda (in advance caustic soda is mixed with weight percent concentration be 10% solution) and carry out neutralization reaction, make pH value reach 2.5, obtain positive sodium titanate.With the positive sodium titanate of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 2.5 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains pure titanic Acid precipitation.91 gram tartrate (purity is in 100%) are added in the pure titanic Acid precipitation, add 45 ml distilled waters, in container, stir, obtain the nano titanium oxide liquid precursor.
Positive metatitanic acid and tartaric chemical equation are as follows:
Embodiment 9: choose titanium sulfate (titanyl sulfate) 260 grams and be main raw material, in this example, 260 gram titanium sulfates (titanyl sulfate) are equivalent to contain 100 gram TiO
2, titanium sulfate (titanyl sulfate) is added ammoniacal liquor carry out neutralization reaction, make pH value reach 2.5, obtain positive titanium acid ammonium.With the positive titanium acid ammonium of distilled water wash, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 1.0 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with distilled water again, makes iron ion content be lower than 10
-5% obtains positive metatitanic acid.460 gram tartrate (purity is in 100%) are added in the pure titanic Acid precipitation, add 45 ml distilled waters, in container, stir, obtain the nano titanium oxide liquid precursor.
Embodiment 10: present embodiment is similar to embodiment 9.In the present embodiment, choose titanium sulfate (titanyl sulfate) 260 grams and be main raw material, in this example, 260 gram titanium sulfates (titanyl sulfate) are equivalent to contain 100 gram TiO
2, titanium sulfate (titanyl sulfate) is added ammoniacal liquor carry out neutralization reaction, make pH value reach 2.5, obtain positive titanium acid ammonium.With deionized water wash titanic acid ammonium, make it be converted into positive metatitanic acid, and make the sodium ions content in the positive metatitanic acid be lower than 10
-3% has washed the back and has regulated pH value to 1.2 with hydrochloric acid, adds 1.0 gram zinc powders, under stirring zinc powder is reacted completely, and regulates pH value to 3 with ammoniacal liquor, washs with deionized water again, makes iron ion content be lower than 10
-5% obtains pure titanic Acid precipitation.680 gram tartrate (purity is in 100%) are added in the pure titanic Acid precipitation, add 65 ml distilled waters, in container, stir, obtain the nano titanium oxide liquid precursor.
Claims (7)
1, a kind of preparation method of nano titanium oxide liquid precursor is characterized in that carrying out according to the following steps:
(1), anatase titanium dioxide or metatitanic acid or titanium sulfate are treated to positive titanate;
(2), the positive titanate of gained is washed, obtain the titanic Acid precipitation with pure water;
(3), can add in the titanic Acid precipitation with the organic complexing agent that titanium ion forms water soluble complex and add pure water, institute's amount of water is contained TiO in the titanic Acid precipitation
20.1～5 times of weight fully reacts the organic complexing agent and the titanic Acid precipitation that are added through stirring, obtains the organic complex of titanium, i.e. the nano titanium oxide liquid precursor.
2, preparation method as claimed in claim 1, it is characterized in that in step (1), adopt alkali fusion that anatase titanium dioxide or metatitanic acid are handled and obtain positive titanate, concrete steps are: in weight part, get 1 part of anatase titanium dioxide, 2～5 parts in caustic soda, or get by what mud scale was measured and measured and contain 1 part of TiO
22～5 parts in metatitanic acid, caustic soda, carried out fusion 1～3 hour with iron ware, finally obtain positive sodium titanate.
3, preparation method as claimed in claim 1, it is characterized in that in step (1), adopt sulfuric acid process that anatase titanium dioxide or metatitanic acid are handled and obtain positive titanate, concrete steps are: in weight part, get 1 part of anatase titanium dioxide, 2～5 parts in the sulfuric acid in 100%, or get by what mud scale was measured and measured and contain 1 part of TiO
21～3 part in metatitanic acid, sulfuric acid in 100%, wherein make vitriolic concentration be formulated as 55%～65%, 130～140 ℃ of reactions 12～16 hours, obtain titanium sulfate solution; Adding ammoniacal liquor or caustic soda carry out neutralization reaction in resulting titanium sulfate solution again, make pH value reach 2.5～3.5, finally obtain positive titanium acid ammonium or positive sodium titanate precipitation.
4, preparation method as claimed in claim 1, it is characterized in that in step (1), adopt following method that titanium sulfate is handled and obtain positive titanate: in titanium sulfate solution, add ammoniacal liquor or caustic soda carries out neutralization reaction, make pH value reach 2.5～3.5, finally obtain positive titanium acid ammonium or positive sodium titanate precipitation.
5, preparation method as claimed in claim 1 is characterized in that in step (2), will contain 100 parts of TiO by what mud scale was measured and measured with pure water
2Positive titanate wash, make it be converted into positive metatitanic acid, and make sodium ion or ammonium ion content in the positive metatitanic acid be lower than 10-3%, washed the back and regulated pH value to 0.5～1.5 with hydrochloric acid, the adding weight part is 0.5～5 part a zinc powder, under stirring zinc powder is reacted completely, regulate pH value to 2.5～3.5 with ammoniacal liquor, wash with pure water again, make iron ion content be lower than 10-5%,, finally obtain pure titanic Acid precipitation.
6, preparation method as claimed in claim 1 is characterized in that in step (3), and the described organic complexing agent that can form water soluble complex with titanium ion is an oxalic acid, in weight ratio, add organic complexing agent consumption be TiO in the positive metatitanic acid
20.5～4 times of content.
7, preparation method as claimed in claim 1 is characterized in that in step (3), and the described organic complexing agent that can form water soluble complex with titanium ion is a tartrate, in weight ratio, add organic complexing agent consumption be TiO in the positive metatitanic acid
20.85～7 times of content.
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| CN100484880C (en) * | 2005-09-22 | 2009-05-06 | 中国科学院理化技术研究所 | Low-temperature crystallized nano titanium dioxide powder and synthesis method of sol |
| CN100531898C (en) * | 2006-06-12 | 2009-08-26 | 中国科学院理化技术研究所 | Preparation method of nano titanium dioxide/silicon dioxide composite photocatalytic sol and transparent photocatalytic film |
| CN102786302A (en) * | 2012-08-22 | 2012-11-21 | 攀枝花学院 | Method for producing barium titanate from titaniferous solution as raw material |
| CN106115775B (en) * | 2016-06-29 | 2017-10-31 | 攀枝花学院 | Adulterate the preparation method of positive metatitanic acid |
| CN108057445A (en) * | 2017-12-21 | 2018-05-22 | 厦门大学 | A kind of methanation catalyst of titaniferous aluminium complex carrier and preparation method thereof |
| CN109364904A (en) * | 2018-12-04 | 2019-02-22 | 大连宜安科技有限公司 | A kind of indoor air pollutants liquid scavenger and preparation method thereof |
| 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 |
| CN116217613A (en) * | 2022-11-30 | 2023-06-06 | 方蕾蕾 | Titanic acid-containing compound and preparation method thereof |
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