CN101671180A - (Sub) supercritical continuous hydro-thermal synthesis process of barium titanate powder - Google Patents
(Sub) supercritical continuous hydro-thermal synthesis process of barium titanate powder Download PDFInfo
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- CN101671180A CN101671180A CN200910019114A CN200910019114A CN101671180A CN 101671180 A CN101671180 A CN 101671180A CN 200910019114 A CN200910019114 A CN 200910019114A CN 200910019114 A CN200910019114 A CN 200910019114A CN 101671180 A CN101671180 A CN 101671180A
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Abstract
The invention provides a (sub) supercritical continuous hydro-thermal synthesis process of barium titanate powder. The process steps comprise titanium source preparation, barium source preparation, reaction in a tubular reactor, cooling in a cooler with high-purification water, further cooling in a ceramic membrane washing device and drying in a spray dryer. The (sub) supercritical continuous hydro-thermal synthesis process has the advantages of simple and feasible process, capability of continuous production, high production efficiency, low cost, excellent barium titanate powder and the like.
Description
Technical field
The present invention relates to (Asia) overcritical continuous hydro-thermal synthesis process of a kind of chemical synthesis process, particularly a kind of barium carbonate powder, belong to electronic ceramics powder body material preparation field.
Background technology
Barium titanate (BaTiO
3) be a kind of ABO of having that finds the earliest
3The typical ferroelectrics of type perovskite crystal structure, it has high-k, low dielectric loss and excellent electric properties such as ferroelectric, piezoelectricity and positive temperature coefficient effect, is widely used in preparing high-permitivity ceramics electrical condenser, laminated ceramic capacitor, PTC thermistor, dynamic RAM, resonator, ultrasonic detector, temperature control sensor etc.
The barium carbonate powder of making laminated ceramic capacitor (MLCC) requires higher relatively at aspects such as granularity and distribution, purity.And the cost pressure of components and parts constantly is transformed on the starting material such as barium titanate medium, thereby the reduction of starting material production cost is also very urgent.In recent years, the price of machine products such as computer, mobile phone keeps falling, and causes the price decline of the average price of MLCC element with annual approximately 5-10%.The cost pressure of components and parts such as MLCC finally can be transformed on the starting material such as barium titanate.
At present, the method that is used for producing barium carbonate powder mainly contains solid-phase synthesis and hydrothermal method etc.Wherein hydrothermal method synthetic barium carbonate powder particle diameter evenly, good dispersity, purity height, active good, be suitable for making MLCC, belong to high-end barium carbonate powder.But traditional hydrothermal method generally adopts the batch still formula to produce, and intermittently hydro-thermal is synthetic all to adopt the still formula as patent CN1830806A, CN 101100310A, CN 1323759A.This method exists reaction time long, and equipment washing is loaded down with trivial details, production efficiency is lower, the more high shortcoming of energy consumption.By contrast, overcritical continuous hydro-thermal synthetic technology has short, advantage such as production efficiency is high, processing condition are easy to control, energy consumption is relatively low of reaction times.And overcritical chemistry also is a kind of " Green Chemistry ", can satisfy the demand of environmental protection aspect.
Summary of the invention
(Asia) the overcritical continuous hydro-thermal synthesis process that the objective of the invention is to avoid the deficiencies in the prior art and a kind of barium carbonate powder is provided.
The technical solution adopted in the present invention is: its concrete processing step is as follows:
(1) preparation titanium source: in the titanium source, add mineralizer or precipitation agent, reaction, preparation titanium solution or titaniferous colloid are put into the titanium source container with the titanium source for preparing, and keep powerful and stir;
(2) preparation barium source: preparation barium compound solution, the barium source container is put in the barium source for preparing, under protection of inert gas, keep powerful and stir;
(3) barium source, titanium source and high purity water are squeezed in the tubular reactor with three high pressure plunger pumps respectively reacted;
(4) slip after reaction finishes enters in the water cooler and cools off with high purity water;
(5) through cooled slurry, squeeze into the ceramic membrane washing device by back pressure valve and further cool off, wash simultaneously, concentrate;
(6) the qualified barium titanate slurry of step (5) gained washing is entered spray-drier and carry out drying.
The titanium source is TiCl
4, metatitanic acid, positive metatitanic acid, TiO
2Powder, TiO
2In colloid, the organic titanium (metatitanic acid tetrem butyl ester, isopropyl titanate etc.) one or more; The barium source is one or more in barium hydroxide, bariumchloride, nitrate of baryta, the barium acetate; Mineralizer or precipitation agent are one or more in ammoniacal liquor, sodium hydroxide, potassium hydroxide, the Tetramethylammonium hydroxide.
Adopt TiCl
4During for the titanium source, with TiCl
4Mix, react with ammoniacal liquor, NH
4OH: TiCl
4(mol ratio) 〉=4 will obtain to such an extent that white gels is washed, concentrated; When the titanium source is organic titanium such as tetrabutyl titanate, titanium isopropylate, with metatitanic acid tetrem butyl ester, isopropyl titanate and water mixed hydrolysis, generate precipitation, washing concentrates; The titanium source is TiO
2Or TiO
2During colloid, do not add precipitation agent or mineralizer.
Temperature of reaction in the tubular reactor is 300～600 ℃, reaction pressure is 10～50Mpa, and the reaction times is 0.1～300 second, and reaction density (in Ti) is 0.01～1mol/L, reactant B a/Ti (mol ratio)=1～4, preheating high purity water flow and the ratio of barium source or titanium source flux be necessary＞and 1.
The technical scheme that the present invention can also adopt has: the temperature of reaction in the tubular reactor is 400～600 ℃, pressure is 25～50Mpa,, can realize in the reaction times that was less than for 1 second that the limit continuous of nano barium carbonate powder is synthetic at reactant B a/Ti (mol ratio) 〉=1.1 o'clock.
The third technical scheme of the present invention is: the temperature of reaction in the tubular reactor is 380～600 ℃, pressure＞15Mpa, and reactant B a/Ti 〉=1.2 can be in 5～300 seconds reaction times, the directly synthetic tetra phase barium titanate powder that obtains different axial ratios.
Tubular reactor preheating high purity water flow is preferably 3～10 with the ratio of barium source or titanium source flux.
Advantage of the present invention is: the technology simple possible, and the production that can even continue, the production efficiency height, cost is low, the barium carbonate powder proterties high-quality of gained etc.
Description of drawings
Fig. 1 is a synthesizer synoptic diagram of the present invention.
Among the figure: 1 is the high purity water container, and 2 is high pressure plunger pump, and 3 is preheater, and 4 is tubular reactor, and 5 is well heater, and 6 is the titanium source container, and 7 is the barium source container, and 8 is water cooler, and 9 is back pressure valve, and 10 is the ceramic membrane washing device, and 11 is spray-drier.
Embodiment
The concrete processing step of (Asia) overcritical continuous hydro-thermal synthesis process of a kind of barium carbonate powder is as follows: (1) preparation titanium source: add mineralizer or precipitation agent in the titanium source, reaction, preparation titanium solution or titaniferous colloid are put into titanium source container 6 with the titanium source for preparing, and keep powerful and stir;
(2) preparation barium source: preparation barium compound solution.Barium source container 7 is put in the barium source for preparing, under protection of inert gas, kept powerful and stir;
(3) barium source, titanium source and high purity water are squeezed in the tubular reactor 4 with three high pressure plunger pumps respectively reacted;
(4) slip after reaction finishes enters in the water cooler 8 and cools off with high purity water;
(5) through cooled slurry, squeeze into ceramic membrane washing device 10 by back pressure valve 9 and further cool off, wash simultaneously, concentrate;
(6) the qualified barium titanate slurry of step (5) gained washing is entered spray-drier 11 and carry out drying.
The titanium source is one or more in TiCl4, metatitanic acid, positive metatitanic acid, TiO2 powder, TiO2 colloid, the organic titanium (metatitanic acid tetrem butyl ester, isopropyl titanate etc.); The barium source is one or more in barium hydroxide, bariumchloride, nitrate of baryta, the barium acetate; Mineralizer or precipitation agent are one or more in ammoniacal liquor, sodium hydroxide, potassium hydroxide, the Tetramethylammonium hydroxide.
When adopting TiCl4 to be the titanium source, TiCl4 is mixed, reacts with ammoniacal liquor, NH4OH: TiCl4 (mol ratio) 〉=4 will obtain to such an extent that white gels is washed, concentrated; When the titanium source is organic titanium such as tetrabutyl titanate, titanium isopropylate, with metatitanic acid tetrem butyl ester, isopropyl titanate and water mixed hydrolysis, generate precipitation, washing concentrates; When the titanium source is TiO2 or TiO2 colloid, do not add precipitation agent or mineralizer.
Temperature of reaction in the tubular reactor 4 is 300～600 ℃, reaction pressure is 10～50Mpa, and the reaction times is 0.1～300 second, and reaction density (in Ti) is 0.01～1mol/L, reactant B a/Ti (mol ratio)=1～4, preheating high purity water flow and the ratio of barium source or titanium source flux be necessary＞and 1.
The technical scheme that the present invention can also adopt has: the temperature of reaction in the tubular reactor 4 is 400～600 ℃, pressure is 25～50Mpa,, can realize in the reaction times that was less than for 1 second that the limit continuous of nano barium carbonate powder is synthetic at reactant B a/Ti (mol ratio) 〉=1.1 o'clock.
The third technical scheme of the present invention is: the temperature of reaction in the tubular reactor 4 is 380～600 ℃, pressure＞15Mpa, and reactant B a/Ti 〉=1.2 can be in 5～300 seconds reaction times, the directly synthetic tetra phase barium titanate powder that obtains different axial ratios.
Tubular reactor 4 preheating high purity water flows are preferably 3～10 with the ratio of barium source or titanium source flux.
High purity water container 1 is placed high purity water; Place titanium solution or the titaniferous colloid for preparing in the titanium source container 6, and keep powerful stirring; Place barium compound solution in the barium source container 7, under protection of inert gas, keep powerful and stir; 4 heating of 5 pairs of tubular reactors of well heater are used in barium source, titanium source and squeeze in the tubular reactor 4 with three high pressure plunger pumps 2 respectively through the high purity water of preheater 3 preheatings and to react in the reaction process; Slip after reaction finishes enters in the water cooler 8 and cools off with high purity water; Cooled high purity water flows into high purity water container 1 and enters response procedures; Through cooled slurry, squeeze into ceramic membrane washing device 10 by back pressure valve 9 and further cool off, wash simultaneously, concentrate; The qualified barium titanate slurry of gained washing enters spray-drier 11 and carries out drying.
Embodiment 1
Taking by weighing 189.69g TiCl4 and 6L concentration is the ammoniacal liquor reaction of 1mol/L, generates white gels.With this gel filtering and washing number time, put into titanium source container reslurry, keep powerful and stir.With 368.11g purity 98% Ba (OH)
28H
2O is dissolved in 5L40 ℃ the high purity water, and keeps powerful the stirring under nitrogen protection.With ram pump raw material and high purity water are squeezed in the tubular reactor in 1: 1: 6 ratio then and reacted, the pilot plunger pumping capacity, guarantee that reactant residence time in tubular reactor is 50S, and to set temperature of reaction be 420 ℃, regulate back pressure valve and guarantee that reaction pressure is 30Mpa.Slip after reaction finishes directly enters spraying drying and carries out solid-liquid separation behind ceramic membrane system purifying.The about 70nm of gained barium carbonate powder particle diameter, crystalline phase is a cube phase.
Embodiment 2
Take by weighing 284g analytical pure titanium isopropylate, follow quick stirring, with its hydrolysis in the beaker that fills the 5L pure water, behind the stirring 10min, the hydrolysate filtering and washing.Hydrolysate after this washing is disperseed to be diluted to volume again with pure water in beaker be 900ml, add the analytical pure nitric acid 47g of concentration 65%, and moisturizing is 1L to volume.Follow quick stirring then, above-mentioned slip is heated up,, obtain transparent TiO in 70 ℃ of insulation 3h
2Colloidal sol.Add the 11.5L high purity water then, make this TiO
2[Ti]=0.08mol/L in the colloidal sol.
Take by weighing 473g purity and be 98% Ba (OH)
28H
2O is dissolved in 80 ℃ of hot pure water of 12L, makes barium hydroxide solution.
With TiO
2Colloidal sol, barium hydroxide solution and high purity water are squeezed in the tubular reactor with ram pump respectively in 1: 1: 5 ratio, and conditioned reaction pressure is 20Mpa, and temperature of reaction is 420 ℃, and the reaction times is 80s.The barium titanate slurry that reacting finishes obtains directly enters spraying drying and carries out solid-liquid separation behind ceramic membrane system purifying.Can obtain the tetra phase barium titanate powder of the about 100nm of particle diameter.
Claims (7)
1, a kind of (Asia) of barium carbonate powder overcritical continuous hydro-thermal synthesis process is characterized in that comprising following steps:
(1) preparation titanium source: in the titanium source, add mineralizer or precipitation agent, reaction, preparation titanium solution or titaniferous colloid are put into the titanium source container with the titanium source for preparing, and keep powerful and stir;
(2) preparation barium source: preparation barium compound solution, the barium source container is put in the barium source for preparing, under protection of inert gas, keep powerful and stir;
(3) barium source, titanium source and high purity water are squeezed in the tubular reactor with three high pressure plunger pumps respectively reacted;
(4) slip after reaction finishes enters in the water cooler and cools off with high purity water;
(5) through cooled slurry, squeeze into the ceramic membrane washing device by back pressure valve and further cool off, wash simultaneously, concentrate;
(6) the qualified barium titanate slurry of step (5) gained washing is entered spray-drier and carry out drying.
2, (Asia) of a kind of barium carbonate powder according to claim 1 overcritical continuous hydro-thermal synthesis process is characterized in that the titanium source is TiCl
4, metatitanic acid, positive metatitanic acid, TiO
2Powder, TiO
2In colloid, the organic titanium (metatitanic acid tetrem butyl ester, isopropyl titanate etc.) one or more; The barium source is one or more in barium hydroxide, bariumchloride, nitrate of baryta, the barium acetate; Mineralizer or precipitation agent are one or more in ammoniacal liquor, sodium hydroxide, potassium hydroxide, the Tetramethylammonium hydroxide.
3, (Asia) of a kind of barium carbonate powder according to claim 1 overcritical continuous hydro-thermal synthesis process is characterized in that preparing in the titanium source procedure: adopt TiCl
4During for the titanium source, with TiCl
4Mix, react with ammoniacal liquor, NH
4OH: TiCl
4(mol ratio) 〉=4 will obtain to such an extent that white gels is washed, concentrated; When the titanium source is organic titanium such as tetrabutyl titanate, titanium isopropylate, with metatitanic acid tetrem butyl ester, isopropyl titanate and water mixed hydrolysis, generate precipitation, washing concentrates; The titanium source is TiO
2Or TiO
2During colloid, do not add precipitation agent or mineralizer.
4, (Asia) of a kind of barium carbonate powder according to claim 1 overcritical continuous hydro-thermal synthesis process, it is characterized in that the temperature of reaction in the tubular reactor is 300～600 ℃, reaction pressure is 10～50Mpa, reaction times is 0.1～300 second, reaction density (in Ti) is 0.01～1mol/L, reactant B a/Ti (mol ratio)=1～4, preheating high purity water flow and the ratio of barium source or titanium source flux be necessary＞and 1.
5, (Asia) of a kind of barium carbonate powder according to claim 1 overcritical continuous hydro-thermal synthesis process, it is characterized in that the temperature of reaction in the tubular reactor is 400～600 ℃, pressure is 25～50Mpa,, can realize in the reaction times that was less than for 1 second that the limit continuous of nano barium carbonate powder is synthetic at reactant B a/Ti (mol ratio) 〉=1.1 o'clock.
6, (Asia) of a kind of barium carbonate powder according to claim 1 overcritical continuous hydro-thermal synthesis process, it is characterized in that the temperature of reaction in the tubular reactor is 380～600 ℃, pressure＞15Mpa, reactant B a/Ti 〉=1.2, can be in 5～300 seconds reaction times, the directly synthetic tetra phase barium titanate powder that obtains different axial ratios.
7, (Asia) of a kind of barium carbonate powder according to claim 1 overcritical continuous hydro-thermal synthesis process is characterized in that the tubular reactor preheating high purity water flow and the ratio of barium source or titanium source flux are preferably 3～10.
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|---|---|---|---|
| CN200910019114A CN101671180A (en) | 2009-09-25 | 2009-09-25 | (Sub) supercritical continuous hydro-thermal synthesis process of barium titanate powder |
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| CN200910019114A CN101671180A (en) | 2009-09-25 | 2009-09-25 | (Sub) supercritical continuous hydro-thermal synthesis process of barium titanate powder |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887540A (en) * | 2011-07-22 | 2013-01-23 | 山东国瓷功能材料股份有限公司 | Ultra (sub) critical hydro-thermal synthesis method and device of high-purity BaTiO3 powder |
| CN103949654A (en) * | 2014-04-02 | 2014-07-30 | 西安交通大学 | Supercritical hydro-thermal synthesis preparation system of nano particles |
| CN109809468A (en) * | 2018-12-28 | 2019-05-28 | 南通奥新电子科技有限公司 | A kind of preparation method and applications of nano barium phthalate |
| CN109928423A (en) * | 2018-12-28 | 2019-06-25 | 南通奥新电子科技有限公司 | A kind of preparation method of the nano barium phthalate for lithium battery |
| CN113753944A (en) * | 2021-10-14 | 2021-12-07 | 福建贝思科电子材料股份有限公司 | Superfine barium titanate powder and preparation method thereof |
-
2009
- 2009-09-25 CN CN200910019114A patent/CN101671180A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887540A (en) * | 2011-07-22 | 2013-01-23 | 山东国瓷功能材料股份有限公司 | Ultra (sub) critical hydro-thermal synthesis method and device of high-purity BaTiO3 powder |
| CN103949654A (en) * | 2014-04-02 | 2014-07-30 | 西安交通大学 | Supercritical hydro-thermal synthesis preparation system of nano particles |
| CN103949654B (en) * | 2014-04-02 | 2015-12-02 | 西安交通大学 | A kind of supercritical water thermal synthesis preparation system of nano particle |
| CN109809468A (en) * | 2018-12-28 | 2019-05-28 | 南通奥新电子科技有限公司 | A kind of preparation method and applications of nano barium phthalate |
| CN109928423A (en) * | 2018-12-28 | 2019-06-25 | 南通奥新电子科技有限公司 | A kind of preparation method of the nano barium phthalate for lithium battery |
| CN113753944A (en) * | 2021-10-14 | 2021-12-07 | 福建贝思科电子材料股份有限公司 | Superfine barium titanate powder and preparation method thereof |
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Open date: 20100317 |