CN109019676A - A kind of method that the precipitation method prepare high-purity Nano-class barium titanate - Google Patents
A kind of method that the precipitation method prepare high-purity Nano-class barium titanate Download PDFInfo
- Publication number
- CN109019676A CN109019676A CN201811176552.2A CN201811176552A CN109019676A CN 109019676 A CN109019676 A CN 109019676A CN 201811176552 A CN201811176552 A CN 201811176552A CN 109019676 A CN109019676 A CN 109019676A
- Authority
- CN
- China
- Prior art keywords
- temperature
- solution
- barium
- barium titanate
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of methods that precipitation method prepare high-purity Nano-class barium titanate, are prepared for a kind of high-purity Nano-class barium titanate by the precipitation method, specifically include that (1) is dissolved；(2) it is co-precipitated；(3) filtration washing；(4) it is sanded spraying；(5) it calcines.Barium titanate prepared by the present invention has the features such as at low cost, crystal grain is small, purity is high, good dispersion.
Description
Technical field
The invention belongs to field of electronic materials, are related to a kind of method that the precipitation method prepare high-purity Nano-class barium titanate.
Background technique
With electronic component miniature requirement, MLCC etc. requires to fine grain, high dispersive barium titanate raw material, high-purity
Degree, inexpensive direction is developed.Existing market major demands be 500nm and 300nm and hereinafter, and solid phase method prepare 300nm and with
Lower complex process, higher cost and dispersion are unevenly；Hydro-thermal method barium titanate granularity is small, is uniformly dispersed, but at high cost.The present invention is logical
The barium titanate for crossing precipitation method preparation is at low cost, and crystal grain is small, is uniformly dispersed, and purity is high fully meets market to 300nm and following crystalline substance
Grain barium titanate demand.
Summary of the invention
Present invention aims to prepare a kind of high-purity Nano-class barium titanate with the precipitation method.
A kind of method that the precipitation method prepare high-purity barium titanate, its step are as follows:
(1) it dissolves: electronic grade barium carbonate powder being added in the dichloro oxygen titanium solution of 1.0 ~ 2.5mol/L under agitation, instead
Barium titanium mixed solution a should be generated, wherein Ba/Ti ratio (molar ratio) is 0.995 ~ 1.005.
(2) it precipitates: using ammonium bicarbonate as precipitating reagent, 2.5 ~ 3.5mol/L ammonium bicarbonate solution being added to by barium with 25-35mL/min flow velocity
In titanium mixed solution in a, the Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea of gross mass 5 ~ 8% are added into barium titanium mixed solution a,
Stop charging when pH >=7, stirs 30min, reaction process is controlled at 35 ~ 42 DEG C；
(3) filtration washing: adding pure water that washing is filtered for multiple times, and chloride ion is detected with silver nitrate, until chloride ion≤10ppm(colorimetric
Method)；
(4) it is sanded spraying: slurry being sanded by sand mill, makes to detect granularity D50≤400nm；With inlet temperature for 250 ~ 300
DEG C, 100 DEG C of outlet temperature spray drying；
(5) calcine: calcination temperature 950 ~ 1000,3 DEG C/min of heating rate keep the temperature 2 ~ 3 hours.
The present invention is reacted with dichloro oxygen titanium solution using solid electronic grade barium carbonate powder, Japanese rock paddy carbon point is added simultaneously
Son sieve and urea, reduce ammonium bicarbonate usage amount, are good for the environment, and slurry with surface there is the rock paddy carbon molecular sieve of porous structure to make
To deposit core, pulp particle is uniformly arranged in rock paddy carbon molecular sieve surface, with regard to shape after pulp particle growth to a certain extent
At the presoma that uniform particle sizes, particle size range are unified, finally calcining removal carbon molecular sieve obtains nano barium phthalate of the present invention.This hair
It is bright to play the role of improving barium carbonate pattern, and the addition of urea has combustion-supporting effect, promotes carbon molecular sieve, ammonium bicarbonate high temperature point
Solution, and it is higher than the common product purity prepared using technical grade barium chloride as the raw material precipitation method to produce product purity；Use sand milling
Technique, the dispersion of product precipitate slurry is more uniform, and spraying rear product Ba/Ti is than more uniform stabilization, and mobility and dispersibility are more
It is good.
Detailed description of the invention
Fig. 1 is the barium carbonate electromicroscopic photograph that embodiment 1 ~ 11 obtains；
Fig. 2 is the barium carbonate electromicroscopic photograph that comparative example 5 obtains.
Specific embodiment
Embodiment 1 ~ 7
By 99.67g(0.5025mol, calcination and the dichloro oxygen titanium that the total 0.5%) barium carbonate of moisture is added slowly to 2.0mol/L are molten
In liquid (250mL) (Ba/Ti=1.005), it is stirred to react until solution is as clear as crystal.Then 3.5mol/L ammonium bicarbonate solution is distinguished
It is gone in above-mentioned barium titanium mixed solution with 25,30,35mL/min flow velocitys, gross mass 5 ~ 8% is added into barium titanium mixed solution a
Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea, until pH is 7 end, control reaction temperature is respectively 37 ± 2,40 ± 2, heat preservation 30
Minute.Using pure water, until chloride ion≤10ppm；After granularity≤300nm is sanded, with 250 DEG C of inlet temperatures, 100 DEG C go out
Mouth temperature spray drying；Start to calcine after drying, 1000 DEG C of calcination temperature, keeps the temperature 2.5 hours.Using nano measurer1.2
Calculate partial size
In comparative example 1,2, be different from embodiment 1 ~ 7: ammonium bicarbonate solution flow velocity is 40 ~ 45mL/min, and reaction temperature is 45 ± 2
DEG C, test result is as follows:
Conclusion: 1-embodiment of embodiment 7 shows Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea that gross mass 5 ~ 8% is added, reaction
Process control temp is 35 ~ 42 DEG C, and 25-35mL/min flow velocity can obtain that crystal grain is small, and be uniformly dispersed good, environmentally friendly effect.
Embodiment 8 ~ 13
By 99.17g(0.5mol, calcination is added slowly to the dichloro oxygen titanium solution of 1.0mol/L with the total 0.5%) barium carbonate of moisture
In (500mL) (Ba/Ti=1.000), it is stirred to react until solution is as clear as crystal.Then by 2.5mol/L ammonium bicarbonate solution with 25mL/
Min flow velocity is gone in above-mentioned barium titanium mixed solution, and the Japanese rock paddy carbon point of gross mass 5 ~ 8% is added into barium titanium mixed solution a
Sub- sieve and 2 ~ 3% urea, until pH is 7 end, 40 ± 2 DEG C of reaction temperature of control keeps the temperature 30 minutes.Using pure water, until
Chloride ion≤10ppm；After granularity≤300nm is sanded, with 300 DEG C of inlet temperatures, 100 DEG C of outlet temperature spray drying；After drying
Start to calcine, 950 ~ 1000 DEG C of calcination temperature, keeps the temperature 2 ~ 3 hours.Partial size is calculated using nano measurer1.2.
In comparative example 3,4, it is different from embodiment 8 ~ 13: does not add Japanese rock paddy carbon molecular sieve and urea, calcining temperature
At 1020 ~ 1080 DEG C, other are same as embodiment 1 ~ 7 for degree control.
Comparative example 5:
By 99.67g(0.5025mol, calcination and the dichloro oxygen titanium that the total 0.5%) barium carbonate of moisture is added slowly to 2.6mol/L are molten
In liquid (500mL) (Ba/Ti=1.005), it is stirred to react until solution is as clear as crystal.Then by 4.0mol/L ammonium bicarbonate solution with
30mL/min flow velocity is gone in above-mentioned barium titanium mixed solution, until pH is 7 end, 40 ± 2 DEG C of reaction temperature of control, heat preservation 30
Minute.Using a large amount of pure waters, until chloride ion≤10ppm；After granularity≤300nm is sanded, with 280 DEG C of inlet temperatures, 100
The spray drying of DEG C outlet temperature；Start to calcine after drying, 1000 DEG C of calcination temperature, keeps the temperature 2.5 hours.Test b a/Ti=1.002,
Partial size 140nm is calculated using nano measurer1.2, electromicroscopic photograph display is reunited serious.
Test result is as follows:
Conclusion: 8-embodiment of embodiment 13 shows the Japanese rock paddy carbon molecules that gross mass 5 ~ 8% is added into barium titanium mixed solution a
Sieve and 2 ~ 3% urea, calcination temperature control between 950 ~ 1000 DEG C, and it is small to obtain crystal grain, are uniformly dispersed good, environmentally friendly
Effect.In addition, this patent is as follows through cost accounting:
1. this patent raw material barium carbonate and titanium tetrachloride, ammonium bicarbonate or urea are tetragonal phase finished product after reaction filtration washing sintering,
20000 yuan/ton of cost；
2. using conventional high-tension hydro-thermal method technique, with barium hydroxide, metatitanic acid is raw material, and one-pot production capacity is low；Reaction product is
Cubic phase need to wash calcining and prepare tetragonal phase；And the tetragonal phase Electronic Speculum granularity > 300nm being typically prepared, cost is 30000
Yuan/ton；300nm uses water and alcohol or other organic matters to be molten with nanometer grade tetragonal-phase barium titanate prepared by hydro-thermal next time
Agent, preparation cost is at 50000 yuan/ton.
Claims (3)
1. a kind of method that precipitation method prepare high-purity Nano-class barium titanate, it is characterised in that following steps:
(1) it dissolves: electronic grade barium carbonate powder is added in the dichloro oxygen titanium solution of 1.0 ~ 2.5mol/L, it is mixed that reaction generates barium titanium
Close solution a；
(2) it precipitates: using ammonium bicarbonate as precipitating reagent, 2.5 ~ 3.5mol/L ammonium bicarbonate solution being added to by barium titanium with 25-35mL/min flow velocity and is mixed
It closes in solution a, the Japanese rock paddy carbon molecular sieve and 2 ~ 3% urea of gross mass 5 ~ 8%, pH >=7 is added into barium titanium mixed solution a
When stop charging, stir 30min, be made slurry b；
(3) filtration washing: adding pure water that washing is filtered for multiple times, and chloride ion is detected with silver nitrate, until chloride ion≤10ppm；
(4) it is sanded spraying: slurry being sanded by sand mill, makes to detect D50 granularity≤400nm；With inlet temperature for 250 ~ 300
DEG C, 100 DEG C of outlet temperature spray drying；
(5) it calcines:, temperature 950 ~ 1000,3 DEG C/min of heating rate keeps the temperature 2 ~ 3 hours.
2. solution temperature≤45 DEG C according to claim 1, are guaranteed using cooling water temperature in step (1) course of dissolution, and
Ba/Ti ratio (molar ratio) is 0.995 ~ 1.005.
3. according to claim 1, step (2) precipitating reagent ammonium bicarbonate solution temperature is 30 ~ 40 DEG C, concentration is 2.5 ~ 4.0mol/
L, reaction temperature are controlled at 35 ~ 42 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811176552.2A CN109019676B (en) | 2018-10-10 | 2018-10-10 | Method for preparing high-purity nano-grade barium titanate by precipitation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811176552.2A CN109019676B (en) | 2018-10-10 | 2018-10-10 | Method for preparing high-purity nano-grade barium titanate by precipitation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109019676A true CN109019676A (en) | 2018-12-18 |
| CN109019676B CN109019676B (en) | 2022-03-11 |
Family
ID=64616415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811176552.2A Active CN109019676B (en) | 2018-10-10 | 2018-10-10 | Method for preparing high-purity nano-grade barium titanate by precipitation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109019676B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772743A (en) * | 2021-09-30 | 2021-12-10 | 青岛天尧新材料有限公司 | Preparation method of manganese cobalt composite oxide powder |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948152A (en) * | 2006-11-10 | 2007-04-18 | 清华大学 | High purity ultra fine zirconium biboride powder and its preparation method |
| KR20130017190A (en) * | 2011-08-10 | 2013-02-20 | 삼성정밀화학 주식회사 | Methods of coating the surface of barium titanic oxide and barium titanic oxide prepared by the same |
| CN103979600A (en) * | 2014-05-30 | 2014-08-13 | 上海沃凯生物技术有限公司 | Preparation method of ultrathin copper oxide powder |
| CN106966426A (en) * | 2017-04-21 | 2017-07-21 | 常州市好利莱光电科技有限公司 | A kind of preparation method of nanoporous stannous oxide |
| CN107555473A (en) * | 2017-09-28 | 2018-01-09 | 洛阳理工学院 | A kind of nanometer BaTiO3Raw powder's production technology |
| CN108046794A (en) * | 2017-12-08 | 2018-05-18 | 中国科学院上海硅酸盐研究所 | The method that metatitanic acid yttrium crystalline ceramics is prepared using Co deposited synthesis powder |
| CN108579715A (en) * | 2018-05-15 | 2018-09-28 | 徐靖才 | A kind of preparation method of porous easily separated nano titania catalyst |
-
2018
- 2018-10-10 CN CN201811176552.2A patent/CN109019676B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948152A (en) * | 2006-11-10 | 2007-04-18 | 清华大学 | High purity ultra fine zirconium biboride powder and its preparation method |
| KR20130017190A (en) * | 2011-08-10 | 2013-02-20 | 삼성정밀화학 주식회사 | Methods of coating the surface of barium titanic oxide and barium titanic oxide prepared by the same |
| CN103979600A (en) * | 2014-05-30 | 2014-08-13 | 上海沃凯生物技术有限公司 | Preparation method of ultrathin copper oxide powder |
| CN106966426A (en) * | 2017-04-21 | 2017-07-21 | 常州市好利莱光电科技有限公司 | A kind of preparation method of nanoporous stannous oxide |
| CN107555473A (en) * | 2017-09-28 | 2018-01-09 | 洛阳理工学院 | A kind of nanometer BaTiO3Raw powder's production technology |
| CN108046794A (en) * | 2017-12-08 | 2018-05-18 | 中国科学院上海硅酸盐研究所 | The method that metatitanic acid yttrium crystalline ceramics is prepared using Co deposited synthesis powder |
| CN108579715A (en) * | 2018-05-15 | 2018-09-28 | 徐靖才 | A kind of preparation method of porous easily separated nano titania catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772743A (en) * | 2021-09-30 | 2021-12-10 | 青岛天尧新材料有限公司 | Preparation method of manganese cobalt composite oxide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109019676B (en) | 2022-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108910932B (en) | Method for preparing narrow-distribution superfine yttrium oxide by sodium carbonate precipitation | |
| JP4992003B2 (en) | Method for producing metal oxide fine particles | |
| CN103395826B (en) | Preparation method of aluminum doped zinc oxide nano powder | |
| KR20080078864A (en) | Methods for production of metal oxide nano particles, and nano particles and preparations produced thereby | |
| CN109704731B (en) | Preparation method of nano yttrium-stabilized zirconia-alumina composite powder | |
| CN101074116B (en) | Production of superfine mono-dispered nano-zirconium dioxide | |
| CN114014651B (en) | Method for producing nano composite zirconia powder by hydrothermal method | |
| CN106882843B (en) | A kind of preparation method of densification crystal form cobaltosic oxide | |
| CN109019676A (en) | A kind of method that the precipitation method prepare high-purity Nano-class barium titanate | |
| RU2714452C1 (en) | Method of producing powders of zirconium dioxide with a spheroidal shape of particles | |
| CN108793224B (en) | Method for preparing narrow-distribution crystal form yttrium carbonate by sodium carbonate precipitation | |
| CN101077790A (en) | Method for preparing rare-earth oxide by homogenous precipitation method | |
| JP4614197B2 (en) | Method for producing metal oxide short fiber | |
| CN103803623B (en) | A kind of production method of high purity barium carbonate | |
| JPS61141619A (en) | Production of zirconia fine powder | |
| KR101324130B1 (en) | Indium tin oxide powder and manufacturing method of producing the same | |
| KR101334261B1 (en) | A preparation method of zinc oxide by wet precipitation | |
| CN101332506B (en) | Rare-earth cobaltous carbonate powder and manufacture method thereof | |
| CN115340126B (en) | Rare earth zirconate particles and preparation method thereof | |
| JP4673042B2 (en) | Method for producing particulate aluminum hydroxide | |
| JPH09110420A (en) | Production of easily sinterable aluminum oxide powder and yttrium-aluminum garnet powder | |
| JPH0742109B2 (en) | Method for producing indium oxide powder | |
| JP2001270714A (en) | Method for producing yag fine powder | |
| CN118324174A (en) | Preparation process of high-purity lutetium oxide powder | |
| KR100503857B1 (en) | Preparation of Nano-sized Crystalline Titanic Acid Barium Powder from Aqueous Titanium Tetrachloride and Barium Chloride Solutions Prepared by Use of Inorganic Acids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |