CN1110958A - High pureness super fined titanate and its sosoloid synthetic process - Google Patents
High pureness super fined titanate and its sosoloid synthetic process Download PDFInfo
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- CN1110958A CN1110958A CN 94104830 CN94104830A CN1110958A CN 1110958 A CN1110958 A CN 1110958A CN 94104830 CN94104830 CN 94104830 CN 94104830 A CN94104830 A CN 94104830A CN 1110958 A CN1110958 A CN 1110958A
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- sosoloid
- titanium dioxide
- ammonia
- slurries
- titanate
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Abstract
The process for cynthesizing the sosoloid of titanates of such elements as Ba, Sr, Pb and Ca features that the Ti source of sosoloid uses the purified hydrated TiO2 and includes proportionally preparing grout, passing ammonia and CO2 through the grout at different flow speeds to generate precursor deposition of sosoloid, filter, washing, drying, breaking, and calcining at 750-1150 deg.C for 1.5-4 hrs to obtain powdered matrix needed by high-quality ceramic capacitor and PTC thermosensitive resistor.
Description
The present invention relates to the synthetic of the single thing phase titanate of elements such as barium, strontium, lead, calcium and sosoloid thereof, particularly high-purity fine strontium-barium titanate sosoloid, Ba
1-xSr
xTiO
3(0≤X≤1) and lead barium titanate sosoloid Ba
1-yPb
yTiO
3The new synthetic process of (0＜Y≤1) powder.The electronic ceramics element that is the matrix made by above-mentioned sosoloid powder has the utmost point to use widely in industrial electrical equipment and household electrical appliance.As except that being used to make ceramic condenser, the piezoelectric ceramics, also be widely used in overheat protector, thermostatical heating element, program-controlled telephone overcurrent protector, motor starting device, compressor for refrigeration starter and color TV magnet exterminator of making Temperature Detector, temperature regulator, temperature equilibrator, temperature indicator, electronics or the like.Along with the development of electronic industry, be to grow with each passing day to the demand of the above-mentioned sosoloid powder of cheap high-purity fine.
(spy opens clear 6191 to Japanese Patent (1,2), 015 and the flat 1-167227 of Te Kai) make and to mention in the titanium source that titanate and sosoloid thereof adopted and using sulfated method is produced titanium dioxide intermediate hydrated titanium dioxide (metatitanic acid), also adopting Titanium White Production By Sulfuric Acid Process intermediate metatitanic acid in people's patents (3) (publication number CN1077695A) such as Ma Shiming is the titanium source of synthesizing titanate.In the document 1 and 2, employed metatitanic acid only mentions with the way of deionized water wash and removes wherein sulfate radical that this way is to be difficult to sulfate radical is eased down to desired degree; In addition, synthetic used precipitation agent is the ammonia soln of volatile salt or bicarbonate of ammonia, and salt such as barium, strontium adopt the respective element muriate.Adopt bariumchloride for barium salt, though cheap on the strontium salt employing strontium chloride price, precipitating adsorbed chlorion is to embarrass water washing to remove, so that the residual chlorine in the product influences the electrical property of element.Document 3 adopts the metatitanic acid synthesizing titanate, but needs to use a large amount of hydrogen peroxide, and the hydrogen peroxide price is quite high, and from cost consideration, this hinders industrializing implementation.
The object of the present invention is to provide the novel process of a kind of synthetic high-purity fine titanate and sosoloid thereof, to overcome the above-mentioned shortcoming and defect part that exists in the prior art.
The object of the present invention is achieved like this:
In reaction vessel, (hydrated titanium dioxide (contains TiO to add appropriate amount of deionized water with Production By Sulfuric Acid Process Cornstarch intermediate hydrated titanium dioxide
2% ≈ 30): 1: 2～8(of water ≈ weight ratio)), stir into homogeneous slurry after, logical ammonia or add ammoniacal liquor, make slurries PH＞10, continue to stir 1～2 hour, filter, filter cake is pulled an oar again, lead to ammonia again or add ammoniacal liquor and make slurries PH＞10, stirring, filtration, repeated washing like this, till sulfate ion is can not check in the inspection of filtrate adding bariumchloride nitric acid liquid, filter, promptly get the hydrated titanium dioxide of purifying.
With the hydrated titanium dioxide of purifying in reaction vessel and analyze its content of titanium dioxide, stoichiometric ratio adding barium and/or strontium by the synthetic sosoloid chemical formula of institute, or barium and/or plumbous nitrate or acetate, add appropriate amount of deionized water, in room temperature to 60 ℃ temperature range, under agitation logical simultaneously ammonia and carbon dioxide gas, ammonia flow velocity: carbon dioxide gas flow velocity＞2: 1, up to barium and/or strontium ion, or barium and/or lead ion precipitation fully till (with unsaturated carbonate ammonium fluid inspection).With precipitation with deionized water wash 3-4 time that contains volatile salt liquid, unloading filter cake dries under 80-120 ℃ of temperature, smashs to pieces, 750-1150 ℃ of temperature lower calcination 1.5～4 hours, the pellet mill be will calcine at last 24 hours, high-purity fine titanate and sosoloid (Ba thereof that detrimental impurity content such as iron, sodium, potassium and magnesium all meet high quality components and parts manufacturing requirement promptly got
1-xSr
xTiO
3, 0≤X≤1; Ba
1-yPb
yTiO
3, 0＜Y≤1) and powder.
Fig. 1 is the inventive method institute synthetic solid-solution powder method X-ray diffraction collection of illustrative plates: a.BaTiO
3Collection of illustrative plates; B.Ba
0.75Sr
0.25TiO
3Collection of illustrative plates; C.Ba
0.5Sr
0.5TiO
3Collection of illustrative plates; D.Ba
0.25Sr
0.75TiO
3Collection of illustrative plates; E.SrTiO
3Collection of illustrative plates; F.PbTiO
3Collection of illustrative plates.
The purify technology of hydrated titanium dioxide of the present invention is simple, and equipment adopts original synthetic equipment, purifies that to consume mainly be ammonia and deionized water, and expense is cheap.
It is that precipitating reagent is that the average particle diameter of granular precursor low and that generate is little than the ammoniacal liquor with ammonium carbonate or carbonic hydroammonium or ammonium oxalate for the precipitating reagent expense that the present invention adopts ammonia and carbon dioxide, and narrow distribution range.
The product that technology of the present invention produces is of high quality and at a reasonable price, wherein objectionable impurities sodium, potassium, iron and The content of the elements such as magnesium all meets high-quality electronic ceramics element and makes requirement.
Technology of the present invention is suitable for large-scale industrial production, and environment is not polluted.
Titanium White Production By Sulfuric Acid Process intermediate hydrated titanium dioxide (is contained TiO
2% ≈ 30) contain in the reaction vessel, after adding appropriate amount of deionized water (hydrated titanium dioxide: 1: 2～8(of water ≈ weight ratio)) making beating and making into homogeneous slurry, logical ammonia or add ammoniacal liquor, make slurries PH＞10, continue to stir 1-2 hour, filter, filter cake is pulled an oar again, lead to ammonia again or add ammoniacal liquor, make slurries PH＞10, continue again to stir, filter, so repeated washing filters till sulfate ion is can not check in the nitric acid liquid inspection that filtrate adds bariumchloride, promptly gets the hydrated titanium dioxide of purifying.
The 199mol hydrated titanium dioxide of having purified is contained in reaction vessel, add about 150 liters of deionized water, after making beating makes into homogeneous slurry, add nitrate of baryta 199mol in room temperature and under stirring, then, feed ammonia and carbon dioxide gas simultaneously, the ammonia flow velocity: carbonic acid gas flow velocity＞2: 1, till barium ion precipitation in slurries is complete (whether precipitate fully with unsaturated carbonate ammonium fluid inspection barium ion, synthesizing approximately needs 4-6 hour).Sedimentation and filtration, filter cake unloads filter cake and dries under 80 ℃ of temperature with the deionized water making beating washing that contains volatile salt 3 times (about 200 liters of each water), smash to pieces, 1050 ℃ of temperature lower calcinations 2 hours, then with its ball milling 24 hours, barium titanate product 42Kg.
Embodiment 2 synthetic Ba
0.75Sr
0.25TiO
3
Hydrated titanium dioxide is purified with embodiment 1.The 195.6mol hydrated titanium dioxide of having purified is contained in reaction vessel, add about 200 liters of deionized water, after making beating makes into homogeneous slurry,, add nitrate of baryta 146.7mol in room temperature and under stirring, strontium nitrate 48.9mol, then, feed ammonia and carbon dioxide gas simultaneously, the ammonia flow velocity: carbonic acid gas flow velocity＞2: 1, till barium in slurries, strontium ion precipitate fully (whether precipitate fully with unsaturated carbonate ammonium fluid inspection barium, strontium ion, synthesizing approximately needs 4-6 hour).Sedimentation and filtration, filter cake unload filter cake with the deionized water making beating washing that contains volatile salt 3 times (about 200 liters of each waters) dries under 120 ℃ of temperature, smashs to pieces, and 1150 ℃ of temperature lower calcinations 1.5 hours, ball milling was 24 hours then, Ba
0.75Sr
0.25TiO
3Product 39.2Kg.
Embodiment 3 synthetic Ba
0.5Sr
0.5TiO
3
Hydrated titanium dioxide is purified with embodiment 1.The 215.4mol hydrated titanium dioxide of having purified is contained in reaction vessel, add about 200 liters of deionized water, after making beating makes into homogeneous slurry,, add nitrate of baryta 107.7mol in room temperature and under stirring, strontium nitrate 107.7mol, then, feed ammonia and carbon dioxide gas simultaneously, the ammonia flow velocity: carbonic acid gas flow velocity＞2: 1, till barium in slurries, strontium ion precipitate fully (whether precipitate fully with unsaturated carbonate ammonium fluid inspection barium, strontium ion, synthesizing approximately needs 4-6 hour).Sedimentation and filtration, filter cake unload filter cake with the deionized water making beating washing that contains volatile salt 3 times (about 200 liters of each waters) dries under 100 ℃ of temperature, smashs to pieces, and 1000 ℃ of temperature lower calcinations 3 hours, ball milling was 24 hours then, Ba
0.5Sr
0.5TiO
3Product 40.75Kg.
Embodiment 4 synthetic Ba
0.25Sr
0.75TiO
3
Hydrated titanium dioxide is purified with embodiment 1.The 206.4mol hydrated titanium dioxide of having purified is contained in reaction vessel, add about 200 liters of deionized water, after making beating makes into homogeneous slurry,, add nitrate of baryta 51.6mol in room temperature and under stirring, strontium nitrate 154.8mol, then, feed ammonia and carbon dioxide gas simultaneously, the ammonia flow velocity: carbonic acid gas flow velocity＞2: 1, till barium in slurries, strontium ion precipitate fully (whether precipitate fully with unsaturated carbonate ammonium fluid inspection barium, strontium ion, synthesizing approximately needs 4-6 hour).Sedimentation and filtration, filter cake unload filter cake with the deionized water making beating washing that contains volatile salt 3 times (about 200 liters of each waters) dries under 90 ℃ of temperature, smashs to pieces, and 1050 ℃ of temperature lower calcinations 2 hours, ball milling was 24 hours then, Ba
0.25Sr
0.75TiO
3Product 36.4Kg.
Embodiment 5 synthetic SrTiO
3
Hydrated titanium dioxide is purified with embodiment 1.The 212.6mol hydrated titanium dioxide of having purified is contained in reaction vessel, add about 200 liters of deionized water, after making beating makes into homogeneous slurry, 60 ℃ and stir under, add strontium nitrate 212.6mol, then, feed ammonia and carbon dioxide gas simultaneously, the ammonia flow velocity: carbonic acid gas flow velocity＞2: 1, till the strontium ion precipitation in slurries is complete (whether precipitate fully with unsaturated carbonate ammonium fluid inspection strontium ion, synthesizing approximately needs 4-6 hour).Sedimentation and filtration, filter cake unload filter cake with the deionized water making beating washing that contains volatile salt 3 times (about 200 liters of each waters) dries under 110 ℃ of temperature, smashs to pieces, and 1050 ℃ of temperature lower calcinations 2 hours, ball milling was 24 hours then, SrTiO
3Product 36.8Kg.
Embodiment 6 synthetic PbTiO
3
Hydrated titanium dioxide is purified with embodiment 1, the 156.4mol hydrated titanium dioxide of having purified is contained in reaction vessel, add about 150 liters of deionized water, after making beating makes into homogeneous slurry, in room temperature and under stirring, add lead nitrate 156.4mol, then, feed ammonia and carbon dioxide gas simultaneously, the ammonia flow velocity: carbonic acid gas flow velocity＞2: 1, till lead ion precipitation in slurries is complete (whether precipitate fully with unsaturated carbonate ammonium fluid inspection lead ion, synthesizing approximately needs 4-6 hour).Sedimentation and filtration, filter cake unload filter cake with the deionized water making beating washing that contains volatile salt 3 times (about 200 liters of each waters) dries under 80 ℃ of temperature, smashs to pieces, and 750 ℃ of temperature lower calcinations 3 hours, ball milling was 24 hours then, PbTiO
3Product 43.2Kg.
Claims (4)
1, a kind of high-purity fine titanate [Ba
1-xSr
xTiO
3(O≤X≤1), Ba
1-yPb
yTiO
3(O＜Y≤1)] and sosoloid synthetic process, it is characterized in that adopting hydrated titanium dioxide (being the intermediate of Titanium White Production By Sulfuric Acid Process) to be the titanium source through purifying, by the stoichiometric ratio of chemical formula of the synthetic sosoloid amount of getting each element compound respectively be mixed with slurries, in room temperature to 60 ℃ scope under agitation, with ammonia and carbon dioxide gas is the precipitation agent that generates the presoma of above-mentioned sosoloid, precipitation after filtration, washing, dry, pulverize after, 750～1150 ℃ of calcinings 1.5-4 hour, through 24 hours ball millings.
2, according to described synthetic high-purity fine titanate of claim 1 and sosoloid novel process thereof, it is characterized in that said hydrated titanium dioxide through purifying means the intermediate hydrated titanium dioxide of Titanium White Production By Sulfuric Acid Process, (hydrated titanium dioxide (contains TiO to add appropriate amount of deionized water
2% ≈ 30): 1: 2～8(of water ≈ weight ratio)), stir into homogeneous slurry, lead to ammonia or add ammoniacal liquor, make slurries PH＞10, continue again to stir 1～2 hour, filter, filter cake is pulled an oar again, lead to ammonia again or add ammoniacal liquor, make slurries PH＞10, continue again to stir 1～2 hour, refilter, so repeat with the ammoniacal liquor of PH＞10 washing hydrated titanium dioxide, (with the nitric acid liquid inspection of bariumchloride) till the sulfate ion can not check in inspection in washings.
3, according to described synthetic high-purity fine titanate of claim 1 and sosoloid novel process thereof, it is characterized in that adopting ammonia and carbonic acid gas is precipitation agent, and feed in the slurries contain hydration titanium dioxide, barium salt and/or strontium salt or feed with gas form and contain in the slurries of hydration titanium dioxide, barium salt and lead salt, not baric and/or strontium or not (with unsaturated carbonate ammonium fluid inspection) till baric and/or the lead ion in the filtrate of filtering slurries.
4, according to the novel process of described synthetic high-purity fine titanate of claim 3 and sosoloid thereof, it is characterized in that adopting ammonia and carbonic acid gas is precipitation agent, ammonia flow velocity: carbonic acid gas flow velocity＞2: 1.
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|---|---|---|---|
| CN94104830A CN1036190C (en) | 1994-04-28 | 1994-04-28 | High pureness super fined titanate and its sosoloid synthetic process |
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|---|---|---|---|
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| CN1036190C CN1036190C (en) | 1997-10-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402437C (en) * | 2006-05-19 | 2008-07-16 | 西北工业大学 | Method for preparing titanate ferroelectric powder |
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| JPH0639330B2 (en) * | 1984-01-24 | 1994-05-25 | ソニー株式会社 | Method for producing barium / strontium titanate fine particles |
| CN1007238B (en) * | 1986-09-10 | 1990-03-21 | 南开大学 | Preparation of barium titanate with ilmenite for use electronic elements |
| ATE73739T1 (en) * | 1987-07-02 | 1992-04-15 | Mitsui Petrochemical Ind | PROCESS FOR THE PREPARATION OF BARIUM TITANATES. |
| CN1027634C (en) * | 1991-11-28 | 1995-02-15 | 清华大学 | Producing method for porcelain very-fine powder of thermal-sensitive resistor with positive temp. coefficient |
| CN1030308C (en) * | 1993-04-26 | 1995-11-22 | 复旦大学 | Process for preparation of titanate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402437C (en) * | 2006-05-19 | 2008-07-16 | 西北工业大学 | Method for preparing titanate ferroelectric powder |
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