CN1046684C - Method for preparing lead titanate powder - Google Patents
Method for preparing lead titanate powder Download PDFInfo
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- CN1046684C CN1046684C CN97100355A CN97100355A CN1046684C CN 1046684 C CN1046684 C CN 1046684C CN 97100355 A CN97100355 A CN 97100355A CN 97100355 A CN97100355 A CN 97100355A CN 1046684 C CN1046684 C CN 1046684C
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- titanium
- mixed solution
- plumbous
- solution
- carbonate
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Abstract
The invention discloses a preparation method of lead titanate powder. Lead nitrate and titanium tetrachloride are used as raw materials, carbonate is used as a precipitator, and a liquid phase method is adopted to prepare lead titanate powder. Has the advantages of stable production process, simple and convenient operation, good product quality and low production cost.
Description
The present invention relates to the preparation method of lead titanate.
The preparation method of lead titanate is divided into solid phase method and liquid phase method two classes usually.Solid phase method is to make the plumbous and solid titanium dioxide of the solid oxidation formation lead titanate that reacts under the high temperature about 1300 ℃.Though this method can practical application, some shortcomings are arranged: 1. solid materials mixes with mechanical means, and its homogeneity and consistence are difficult to be guaranteed; 2. Heating temperature is higher, causes the lead titanate powder particle diameter bigger, is generally about 5 microns; 3. plumbous oxide is volatile in heat-processed, causes being difficult to obtain the stable lead titanate powder product of plumbous titanium mol ratio.
Liquid phase method is the method that forms plumbous titanium compound in liquid medium.At present the liquid phase method of bibliographical information is to be precipitation agent with oxalic acid, utilizes the formation of plumbous titanium oxalate coprecipitation thing and the thermolysis of this coprecipitate to prepare lead titanate powder.The disclosed preparation method of Japanese Patent (JP87-72523) made plumbous titanium mixed solution in 1: 1 in molar ratio with Titanium Nitrate and lead nitrate, be that 1: 1 and titanium and oxalic acid mol ratio are the ethanolic soln that 1: 0.5 ratio is made oxalic acid in lead/oxalic acid mol ratio simultaneously, speed with 60 ml/min under constantly stirring is added drop-wise to this oxalic acid solution in the plumbous titanium mixed solution, separates out plumbous titanium oxalate coprecipitation thing.After this coprecipitate filtration, washing, oven dry, the fragmentation, calcined 2 hours down at 700 ℃, promptly get the lead titanate powder product, its rate of recovery is 92%, and diameter of particle is about 3 microns.The plumbous titanium mol ratio of this method products obtained therefrom is comparatively stable, and is better dispersed.Its shortcoming is: 1. the price of oxalic acid is higher, and its consumption is very big, so production cost is higher; 2. the solubleness of plumbous titanium oxalate coprecipitation thing is bigger, so the rate of recovery of lead titanate powder is lower; 3. alcoholic acid is introduced, and the one, increase production cost, the 2nd, can result in hand cramps aspect the security of operation.
It is lower to the purpose of this invention is to provide a kind of production cost, and the rate of recovery is higher, and the liquid phase preparation process of lead titanate powder easy and simple to handle.
Technical scheme of the present invention is as follows:
The present invention includes operations such as precipitation, filtration, washing, drying-pulverizing and calcining; At first, plumbous titanium mixed solution is added drop-wise in the carbon ammonia mixed solution, is settled out plumbous titanium coprecipitate; Then, with this coprecipitate filtration, washing, dry and pulverizing; At last, under 700 ℃ of temperature, this coprecipitate is sintered into the lead titanate powder product.
Plumbous titanium mixed solution is become with the titanyl nitrate solution mixing system by lead nitrate solution.
The method for making of this titanyl nitrate solution is as follows: titanium tetrachloride is added to makes titanium tetrachloride aqueous solution in the water, then, dropping ammonia to pH value is 7, generates the TiO (OH) of white
2Throw out filters it, washs this throw out with deionized water slurrying again; At last, according to titanium: nitric acid (mol ratio) is 1: 10～1: 12, and this throw out is dissolved in the concentrated nitric acid, promptly gets titanyl nitrate solution.TiO in this solution
2+Concentration can be between 0.5～0.8 mol, and concentration of nitric acid can be between 5.0～6.5 mol, and main solubilizing reaction is as follows:
In plumbous titanium mixed solution, mol ratio plumbous and titanium is 0.995: 1～1.005: 1, and lead concentration is 0.25～0.50 mol, and titanium concentration is 0.25～0.50 mol.
Carbon ammonia mixed solution is mixed and made into by carbonate solution and ammoniacal liquor, and wherein, the mol ratio of carbonate and ammoniacal liquor is 1: 8～1: 10, CO
3 2-Concentration is 0.50 mol.This carbonate can be volatile salt or bicarbonate of ammonia.
After plumbous titanium mixed solution and carbon ammonia mixed solution are made respectively, can prepare plumbous titanium coprecipitate by sedimentary method, i.e. the coprecipitate of white lead carbonate and hydrated titanium dioxide, its chemical reaction is as follows:
The way for preparing this lead titanium coprecipitate is as follows: under 10～45 ℃ of temperature, low whipping speed is under 600 rev/mins the continuous stirring, according to Pb: CO
3 2-(mol ratio) is 1: 1.2～1: 1.5 requirement, with 50～100 milliliters/speed of (minute rise) plumbous titanium mixed solution is added drop-wise in the carbon ammonia mixed solution, the i.e. plumbous titanium mixed solution of per minute Dropwise 5 0～100ml in every liter of carbon ammonia mixed solution, till the final pH value of this system is 7～9, then, ageing 2 hours has promptly formed the coprecipitate of white lead carbonate and hydrated titanium dioxide.
Because lead and titanium mix with molecular level in the plumbous titanium mixed solution before precipitation, and PbCO
3Pb (OH)
2Solubility product Ksp be 9.0 * 10
-48, TiO (OH)
2Solubility product Ksp be 7.9 * 10
-54, the solubility product of these two kinds of compounds is all very little, so when plumbous titanium mixed solution was added drop-wise in a large amount of carbon ammonia mixed solutions with certain speed, plumbous and titanium was almost separated out precipitation simultaneously in moment, therefore, the distribution of lead and titanium is very uniform in this coprecipitate.
In mother liquor of precipitation of ammonium, contain a large amount of NH
4NO
3, also contain some impurity in lead, the titanium material, in order to improve the purity of coprecipitate, make coprecipitate and mother liquor after separating with filtration method, with deionized water this coprecipitate is carried out washing of slurrying several times and filtration.Washed filter cake is placed in the baking oven, dried 10 hours down, be ground into meal with polishing then at 80 ℃.At last, this material is placed retort furnace, calcined 2 hours down at 700 ℃, obtain light yellow lead titanate powder, its reaction formula is as follows:
This calcination process comes down to a limit decomposition, limit bonded process.Because distribution plumbous and titanium is very uniform in plumbous titanium coprecipitate, when this coprecipitate decomposes, will form the lead titanate powder of the good tetragonal system structure of homogeneity and consistence, wherein, mol ratio plumbous and titanium is 0.995: 1～1.005: 1.
It is as follows that the present invention and background technology are compared the beneficial effect that is had:
(1) easy and simple to handle.Precipitation process need not strict controlled temperature, can carry out at normal temperatures, and the PH wide ranges, be easy to control.
(2) production cost is low.Material cost with 1 ton of lead titanate powder of method of the present invention preparation is 2.6 ten thousand yuan, and the material cost of oxalate method is more than 30,000 yuan, and this is because the present invention replaces the more expensive oxalic acid of price to do precipitation agent with inexpensive carbonate, and production cost is reduced.
(3) rate of recovery height.Owing to use carbonate deposition complete, almost there is not the material loss, therefore, rate of recovery height.
(4) the plumbous titanium mol ratio in the product is stable.Because the solubility product of two kinds of compounds is all minimum in the plumbous titanium coprecipitate, precipitating action is very complete, and precipitation is to carry out at normal temperatures, and especially calcining temperature is lower, has avoided plumbous volatilization loss, so the plumbous titanium mol ratio in the product is stable.
(5) good product quality.With the prepared lead titanate powder of method of the present invention, its particle diameter is little, and plumbous titanium mol ratio is stable, and homogeneity, consistence and dispersiveness are all good, and the product crystalline form is good tetragonal system structure, and pattern is spherical or subsphaeroidal.Accompanying drawing of the present invention is:
Fig. 1 is the process flow sheet of preparation lead titanate.
Embodiments of the invention are as follows:
Embodiment one:
(1) gets the TiCL that 360 ml concns are 4.363 mol
4The aqueous solution, thin up to 2500 milliliter, under constantly stirring dropping ammonia to system PH be 7, filter it.Filter cake is used 1000 milliliters of deionized waters with deionized water slurrying washing at every turn, washes altogether 3 times.Filter cake dissolves with 1230 milliliters of concentrated nitric acids.Placement is spent the night, and filters it, gets TiO (NO
3)
2Solution.Through demarcating, titanyl nitrate concentration is 0.556 mol.
(2) get the TiO (NO that 625 ml concns are 0.556 mol
3)
2Solution, with 700 ml concns be the Pb (NO of 0.497 mol
3)
2Solution mixes, and makes plumbous titanium mixed solution＜I that lead, titanium concentration are respectively 0.26 mol 〉.
(3) take by weighing 47.6 gram (NH
4)
2CO
3H
2O adds deionized water and is dissolved to 610 milliliters, adds 225 milliliters of strong aquas, makes carbon ammonia mixed solution＜II 〉.
(4) under 16 ℃ of temperature, under constantly stirring with solution＜I join 1 liter of solution＜II with the rate of addition of 100 ml/min in, then, ageing 2 hours, the final PH of system is 7.5.Throw out is carried out vacuum filtration, with 500 milliliters of slurrying washings of deionized water, wash altogether 5 times at every turn.
(5) filter cake with washes clean places 80 ℃ of baking ovens, dries by the fire 10 hours.After the cooling, pulverize it.
(6) throw out with oven dry places 700 ℃ of retort furnaces, calcines 2 hours, gets lead titanate powder 102.8 grams, and the rate of recovery is 97.6%.Through the X-diffraction analysis, crystalline structure is good tetragonal system structure.Through chemical analysis, product purity is 99.5%, and plumbous titanium ratio is 1.00: 1.
Embodiment two:
(1) gets the TiCL that 360 ml concns are 4.363 mol
4The aqueous solution, thin up to 2500 milliliter, under constantly stirring dropping ammonia to system PH be 7.Filter it, filter cake is used 1000 milliliters of deionized waters with deionized water slurrying washing at every turn, washes altogether 3 times.Filter cake dissolves with 1020 milliliters of concentrated nitric acids, and placement is spent the night, and filters, and gets TiO (NO
3)
2Solution.Through demarcating, titanyl nitrate concentration is 0.744 mol.
(2) get the TiO (NO that 930 ml concns are 0.744 mol
3)
2With 610 ml concns be the Pb (NO of 1.13 mol
3)
2Solution mixes, and makes plumbous titanium mixed solution＜I that plumbous titanium concentration is respectively 0.45 mol 〉.
(3) take by weighing 81.7 gram NH
4HCO
3, add deionized water and be dissolved to 965 milliliters, add 690 milliliters of strong aquas, make carbon ammonia mixed solution＜II 〉.
(4) under 30 ℃ of temperature, general＜I under constantly stirring〉join 1 liter of solution＜II with the rate of addition of 50 ml/min〉in, ageing is 2 hours then, and the final PH of system is 9.0.Throw out is carried out vacuum filtration, at every turn with 1000 milliliters of deionized water slurrying washings, totally 5 times.Dry this filter cake down at 80 ℃, pulverize it then.
(5) throw out with oven dry places 700 ℃ of retort furnaces, calcines 2 hours, gets lead titanate powder 205.2 grams, and the rate of recovery is 98.2%.This powder median size is 1.08 microns, and plumbous titanium mol ratio is 0.998: 1, and crystalline structure is good tetragonal system, and the scanning electron microscope photograph shows that morphology microstructure is regular spherical or subsphaeroidal, homogeneity and favorable dispersity.
Claims (3)
1. the preparation method of a lead titanate powder, comprise steps such as precipitation, filtration, washing, drying, pulverizing and calcining, it is characterized in that settling step is that plumbous titanium mixed solution is added in the carbon ammonia mixed solution, be settled out the coprecipitate of white lead carbonate and hydrated titanium dioxide, the precipitation operation and the parameter of white lead carbonate and hydrated titanium dioxide coprecipitate are:
(1) be that 0.995: 1～1.005: 1 plumbous titanium mixed solution is added under whipped state in the carbon ammonia mixed solution with plumbous titanium mol ratio, blending ratio is Pb: co
3 2-Mol ratio is 1: 1.2～1: 1.5, and rate of addition joins in 1 liter of solution (II) or the carbon ammonia mixed solution for the rate of addition with 50～100 ml/min, and stirring velocity is 600 rev/mins;
(2) measure precipitation system acidity, pH value is 7～9 when dropwising;
(3) ageing, digestion time are 2 hours.
2. preparation method as claimed in claim 1 is characterized in that plumbous titanium mixed solution is become with the titanyl nitrate solution mixing system by lead nitrate solution, and lead concentration is 0.25～0.50 mol, and titanium concentration is 0.25～0.50 mol.
3. preparation method as claimed in claim 1 is characterized in that carbon ammonia mixed solution is mixed and made into by carbonate solution and ammoniacal liquor, and wherein the mol ratio of carbonate and ammoniacal liquor is 1: 8～1: 10, and carbonate is meant volatile salt or bicarbonate of ammonia.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100355A CN1046684C (en) | 1997-01-29 | 1997-01-29 | Method for preparing lead titanate powder |
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|---|---|---|---|
| CN97100355A CN1046684C (en) | 1997-01-29 | 1997-01-29 | Method for preparing lead titanate powder |
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| CN1160680A CN1160680A (en) | 1997-10-01 |
| CN1046684C true CN1046684C (en) | 1999-11-24 |
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| CN97100355A Expired - Fee Related CN1046684C (en) | 1997-01-29 | 1997-01-29 | Method for preparing lead titanate powder |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8480780B2 (en) | 2002-02-05 | 2013-07-09 | Ibiden Co., Ltd. | Honeycomb filter for purifying exhaust gases, adhesive, coating material, and manufacturing method of honeycomb filter for purifying exhaust gases |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618889B (en) * | 2009-08-03 | 2011-02-16 | 浙江大学 | Method for preparing lead titanate nano column automatically assembled by perovskite structure nano pieces |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56104715A (en) * | 1980-01-17 | 1981-08-20 | Matsushita Electric Ind Co Ltd | Preparation of lead titanate |
| US4810484A (en) * | 1984-12-28 | 1989-03-07 | Sony Corporation | Method for manufacturing fine lead titanate powders |
-
1997
- 1997-01-29 CN CN97100355A patent/CN1046684C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56104715A (en) * | 1980-01-17 | 1981-08-20 | Matsushita Electric Ind Co Ltd | Preparation of lead titanate |
| US4810484A (en) * | 1984-12-28 | 1989-03-07 | Sony Corporation | Method for manufacturing fine lead titanate powders |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8480780B2 (en) | 2002-02-05 | 2013-07-09 | Ibiden Co., Ltd. | Honeycomb filter for purifying exhaust gases, adhesive, coating material, and manufacturing method of honeycomb filter for purifying exhaust gases |
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| Publication number | Publication date |
|---|---|
| CN1160680A (en) | 1997-10-01 |
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