CN1099726A - High-purity ultra-fine titanate preparing method - Google Patents
High-purity ultra-fine titanate preparing method Download PDFInfo
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- CN1099726A CN1099726A CN 94112239 CN94112239A CN1099726A CN 1099726 A CN1099726 A CN 1099726A CN 94112239 CN94112239 CN 94112239 CN 94112239 A CN94112239 A CN 94112239A CN 1099726 A CN1099726 A CN 1099726A
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Abstract
This invention discloses a preparation method for high-purity superfine titanate. Firstly, soluble organic titanium compatible anion is prepared according to the organic combplexing principle, then the said anion undergoes complex decomposition in water phase with soluble metal salt to obtain homogeneous high-purity superfine organic titanate compound with consistent proportion ratio, and finally, the organic titanate compound is thermo-decomposed under 700-1000 deg.C to obtain high-purity superfine titanate.
Description
The present invention relates to a kind of preparation method of high-purity superfine titanate, particularly prepare the method for high-purity superfine titanate with liquid phase method.
As everyone knows, titanate is the raw material of preparation electronic ceramics, occupies critical role in the contemporary high technology field.The method of producing at present titanate mainly contains three kinds of solid phase method, vapor phase process and liquid phase methods.Wherein, solid phase method is carbonate and titanium dioxide to be carried out high temperature solid state reaction produce, but the titanate grain fineness number that makes is bigger, and purity is low, can not satisfy the needs of high-grade electronic ceramics; Vapor phase process is with volatile metal oxide or metal alkoxide gasification, produce the metallic plasma direct reaction through the higher frequency electromagnetic field and generate the titanate ultra-fine grain, can obtain the product of fine size, purity height, chemical constitution homogeneous, but apparatus expensive, operational difficulty, cost are very high, and only being suitable for research work needs; Liquid phase method is the more general a kind of method, particularly liquid-phase coprecipitation used at present, has advantages such as technology is simple, easy to operate.It adds precipitation agent after normally two kinds of soluble metal ion solution being mixed, and the metal ion co-precipitation is come out, and after filtration, wash, obtain titanate presoma product, and then obtains the titanate product through high temperature pyrolysis.But this method since in precipitation process because of the solubility product K between two metal ion species and the precipitation agent
SpDifference, it is also different with speed to form sedimentary precedence, therefore what obtain is the mixture of the uneven two metal ion species co-precipitation of a class microcosmic, even the ageing by the long period still can not all change into the compound of homogeneous.The present industrial homogenization compound that obtains about 90%, although on macroscopic view, metal ion is than fixing, but because the ununiformity of coprecipitation mixture and the imperfection of conversion reaction, must cause the difference of local component, thereby have influence on the quality of final pyrolysis product, can not satisfy the specification of quality of high-grade electronic ceramics product to the homogeneous high-purity superfine titanate.
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, a kind of method for preparing high-purity superfine titanate is provided, it obtains a class and the organic titanate compound of metering than on all four homogeneous apace by a kind of liquid phase method, organic titanate compound pyrolysis at high temperature then obtains the said high-purity superfine titanate product of the present invention.
Design of the present invention is such:
The contriver by the various organic acids of further investigation on the basis of existence form in the dissociation equilibrium of aqueous phase and the organic acid soln of titanic ion at different PH, proposed a kind of with organic acid at first with TiO
2+Complexing generates the titanium complex anion of solubility, under certain PH, titanium complex anion and soluble metallic salt is carried out replacement(metathesis)reaction at aqueous phase then, generates the organic titanate compound precipitation consistent with measuring ratio of homogeneous.It has overcome the shortcoming that there is microcosmic component ununiformity inevitably in liquid-phase coprecipitation in the past fully.The organic titanate compound of gained after filtration, washing, pyrolysis, can obtain the said homogeneous high-purity superfine titanate of the present invention product.
The present invention also is achieved in that
1. at first titanium tetrachloride is mixed with the aqueous solution that concentration is 0.5～2.0mol/l, size according to coordination ratio adds excessive organic acid complexing agent then, PH with alkali regulation and control solution under stirring condition is 2～4, and titanium in the solution and complexing agent are present in aqueous phase with the form of stable titanium complex anion at this moment.
2. above-mentioned titanium complex anion solution and the solution that contains soluble metallic salt are injected a reactor simultaneously, under agitation carry out replacement(metathesis)reaction, generate the organic titanate compound precipitation of homogeneous, the filtration back is washed till with deionized water does not have C1 in the filter cake
-,, obtain the high pure and ultra-fine organic titanate compound of homogeneous then with filter cake drying under 80～110 ℃.
3. the organic titanate compound with above-mentioned gained places process furnace, speed heat temperature raising to 700～1000 ℃ pyrolysis with 1～10 ℃ of per minute, and be incubated 0.5～2.0hr, and be cooled to room temperature then, promptly obtain the said high-purity superfine titanate product of the present invention.
Said organic acid complexing agent, can be in citric acid, tartrate, oxalic acid, oxysuccinic acid, the Whitfield's ointment one or more, its consumption is looked the size of the coordination ratio between titanium and the organic acid and is different, can choose in mol ratio 1.1～3.5 scopes (organic acid/titanium=1.1～3.5).
Said alkali can be mineral alkali, also can be organic bases, and alkali commonly used is KOH, NaOH, NH
3H
2In O, thanomin, the methylamine one or more.
Said soluble metallic salt can be a kind of in barium salt, strontium salt, calcium salt, manganese salt, magnesium salts, the lead salt, and its suitable concentration is about 1mol/1, and its consumption is 1.0～1.2 times of titanium mole number.
Size for the particulate of regulating and control the organic titanate compound, and generation superfine organic titanate compound precipitation, the present invention adopts being added to two injection methods in the reactor of belt stirrer or by in the flash mixer injecting reactor with the soluble metal salts solution of will containing titanium complex anion solution, and in order to ensure the integrity of replacement(metathesis)reaction, precipitation is ageing 0.5～1.5hr under agitation.
Said filter cake is washed to no C1
-, method that can be routinely is with the AgNO of 0.1mol/L
3Solution detects no AgCl white precipitate.
The superfine titanate product of the high-purity homogeneous that makes according to method of the present invention has component and determines that after testing, wherein the mol ratio between the metal component is 1.000 ± 0.008, and granularity is less than 0.5 μ m, and specific surface is greater than 7m
2/ g can satisfy the high quality requirement of high-grade electronic ceramics product to titanate fully.
Further illustrate content of the present invention below in conjunction with embodiment, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
Adding concentration in a reactor is the TiCl of 1.5mol/1
4Solution 100ml adds Whitfield's ointment 45g, under agitation adds NH
3H
2The PH of O regulator solution is 3～4, generates the complex anion of Whitfield's ointment oxygen titanium, and the cumulative volume of water regulator solution is that 200ml(is called for short solution A).
In another container, add BaCl
22H
2O 37.5g is deployed into the solution that cumulative volume is 200ml (abbreviation solution B) with deionized water.
With above-mentioned solution A and solution B, balancedly add with two injection modes in the reactor of another belt stirrer, under 50～70 ℃ of temperature, carry out replacement(metathesis)reaction, after injection finishes, under the stirring insulation, continue ageing 1 hour, throw out filters after washing to there not being Cl
-,, obtain Whitfield's ointment and close the barium titanate compound then 80～110 ℃ of dryings.
Whitfield's ointment is closed the barium titanate compound place the retort furnace pyrolysis, be warming up to 750 ℃, continue constant temperature 2hr then, can obtain the barium titanate (BaTiO of one of product of the present invention high pure and ultra-fine with 2 ℃/minute speed
3) finished product.
Embodiment 2
Adding concentration in a reactor is the TiCl of 1.5mol/l
4Solution 200ml adds oxalic acid 83g, under agitation adds NaOH, calls in PH=2.5～3 of solution, generates stable titanium oxyoxalate complex anion, and it is that 300ml(is called for short solution A that the water allotment makes the cumulative volume of solution).
In a container, add SrCl
2(strontium chloride) 90g is deployed into the solution (abbreviation solution B) of 300ml with deionized water.
Above-mentioned solution A and solution B are injected the reactor of a belt stirrer by a quick microcosmic mixing tank, carry out replacement(metathesis)reaction under 50～70 ℃ of temperature, inject and continue to stir insulation ageing 1.5hr again after finishing, throw out filters after washing to there not being Cl
-,, obtain oxalic acid and close the strontium titanate compound then 80～110 ℃ of dryings.
Oxalic acid is closed the strontium titanate compound place a retort furnace pyrolysis, and be warming up to 850 ℃, 850 ℃ of following constant temperature 1.5 hours, can obtain one of product of the present invention high pure and ultra-fine metatitanic acid strontium (SrTiO then with the speed of 2 ℃ of per minutes
3) finished product.
Embodiment 3
Adding concentration in a reactor is the TiCl of 1.5mol/l
4Solution 200ml adds tartrate 90g, under agitation adds NH
3H
2O, and the PH=2 of regulator solution～3 generate the complex anion of tartrate oxygen titanium, and it is that 300ml(is called for short solution A that the water allotment makes the cumulative volume of solution).
In a container, add Pb(NO
3)
2, the solution 300ml(that makes 1.03mol/l with the deionized water allotment is called for short solution B).
Solution A and solution B are added the reactor of another belt stirrer in the mode of two injections, carry out replacement(metathesis)reaction under 50～70 ℃ of temperature, add and continue to stir insulation ageing 1hr again after finishing, throw out filters after washing to there not being Cl
-, dry under 80～110 ℃ then, obtain tartrate and close the lead titanate compound.
Above-mentioned tartrate is closed the lead titanate compound place the retort furnace pyrolysis, and be warming up to 950 ℃ with the speed of 3 ℃ of per minutes, constant temperature 1 hour under this temperature can obtain one of product of the present invention high pure and ultra-fine lead titanate (PbTiO then
3) finished product.
Obviously, according to design of the present invention, relevant chemist all can synthesize other high-purity superfine titanate product easily.
Claims (7)
1, a kind of preparation method of high-purity superfine titanate is characterized in that:
(1) regulates and control under the condition of pH value of solution=2～4 with alkali, generate the complex anion of water miscible organic acid oxygen titanium in the aqueous phase complexing by organic acid and titanium tetrachloride;
(2) complex anion of organic acid oxygen titanium is carried out replacement(metathesis)reaction with water miscible metal-salt under the condition of 50～70 ℃ of temperature, generates the organic titanate compound precipitation consistent with measuring ratio of homogeneous, and filtered water is washed till no Cl then
-, and dry under 80～110 ℃, obtain high pure and ultra-fine organic titanate compound;
(3) high pure and ultra-fine organic titanate compound pyrolysis under hot conditions obtains the said high-purity superfine titanate product of the present invention.
2, the method for claim 1, the concentration that it is characterized in that the titanium tetrachloride of aqueous phase is 0.5～2mol/1.
3,, it is characterized in that said organic acid is one or more in oxalic acid, tartrate, citric acid, Whitfield's ointment, the oxysuccinic acid as the described method of one of claim 1-2.
4, as the described method of one of claim 1-3, it is characterized in that mol ratio is 1.1～3.5 between organic acid and the titanium tetrachloride, decide on the size of the coordination ratio between organic acid and the titanium.
5, as the described method of one of claim 1-4, it is characterized in that regulating and control the used alkali in PH=2～4 of solution, can be mineral alkali, also can be organic bases, alkali commonly used is NaoH, KOH, NH
3H
2In O, methylamine, the thanomin one or more.
6,, it is characterized in that said water-soluble metal salt is a kind of in barium salt, strontium salt, lead salt, manganese salt, the magnesium salts as the described method of one of claim 1-5.
7, as the described method of one of claim 1-6, it is characterized in that the high temperature pyrolysis condition of said organic titanate compound is warming up to 700～1000 ℃ for the speed with 1～10 ℃ of per minute, under this temperature, continue insulation pyrolysis 0.5～2hr then.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112239 CN1034997C (en) | 1994-07-22 | 1994-07-22 | High-purity ultra-fine titanate preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112239 CN1034997C (en) | 1994-07-22 | 1994-07-22 | High-purity ultra-fine titanate preparing method |
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|---|---|
| CN1099726A true CN1099726A (en) | 1995-03-08 |
| CN1034997C CN1034997C (en) | 1997-05-28 |
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| CN 94112239 Expired - Fee Related CN1034997C (en) | 1994-07-22 | 1994-07-22 | High-purity ultra-fine titanate preparing method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060324A (en) * | 2010-11-11 | 2011-05-18 | 刘秦 | Method for preparing doped barium titanate powder through wet process |
| CN102173779A (en) * | 2011-01-06 | 2011-09-07 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Method for preparing titanium composite oxide |
| CN101231348B (en) * | 2007-01-24 | 2011-12-28 | 王德强 | Liquid phase chemical synthesis one class optical filming material |
| CN101525151B (en) * | 2009-03-20 | 2013-09-04 | 仙桃市中星电子材料有限公司 | Manufacturing technique for high-purity electronic grade strontium titanate |
| CN106631004A (en) * | 2016-12-26 | 2017-05-10 | 湖南先导电子陶瓷科技产业园发展有限公司 | Technology for preparing high-purity superfine barium titanate by improved liquid-phase settling method |
| CN110436918A (en) * | 2019-07-16 | 2019-11-12 | 桂林电子科技大学 | A kind of method of tartaric acid technique preparation nanometer tetra phase barium titanate powder |
| CN111638212A (en) * | 2020-06-15 | 2020-09-08 | 江南大学 | Method for detecting content of glucose-6-phosphate based on nano enzyme |
-
1994
- 1994-07-22 CN CN 94112239 patent/CN1034997C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101231348B (en) * | 2007-01-24 | 2011-12-28 | 王德强 | Liquid phase chemical synthesis one class optical filming material |
| CN101525151B (en) * | 2009-03-20 | 2013-09-04 | 仙桃市中星电子材料有限公司 | Manufacturing technique for high-purity electronic grade strontium titanate |
| CN102060324A (en) * | 2010-11-11 | 2011-05-18 | 刘秦 | Method for preparing doped barium titanate powder through wet process |
| CN102060324B (en) * | 2010-11-11 | 2013-04-24 | 刘秦 | Method for preparing doped barium titanate powder through wet process |
| CN102173779A (en) * | 2011-01-06 | 2011-09-07 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Method for preparing titanium composite oxide |
| CN102173779B (en) * | 2011-01-06 | 2013-01-02 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Method for preparing titanium composite oxide |
| CN106631004A (en) * | 2016-12-26 | 2017-05-10 | 湖南先导电子陶瓷科技产业园发展有限公司 | Technology for preparing high-purity superfine barium titanate by improved liquid-phase settling method |
| CN110436918A (en) * | 2019-07-16 | 2019-11-12 | 桂林电子科技大学 | A kind of method of tartaric acid technique preparation nanometer tetra phase barium titanate powder |
| CN111638212A (en) * | 2020-06-15 | 2020-09-08 | 江南大学 | Method for detecting content of glucose-6-phosphate based on nano enzyme |
| CN111638212B (en) * | 2020-06-15 | 2021-07-27 | 江南大学 | Method for detecting content of glucose-6-phosphate based on nano enzyme |
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| Publication number | Publication date |
|---|---|
| CN1034997C (en) | 1997-05-28 |
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