CN1243691C - Method for preparing barium titanate powder with metatitanic acid as raw material of titanium - Google Patents
Method for preparing barium titanate powder with metatitanic acid as raw material of titanium Download PDFInfo
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- CN1243691C CN1243691C CN 200410022425 CN200410022425A CN1243691C CN 1243691 C CN1243691 C CN 1243691C CN 200410022425 CN200410022425 CN 200410022425 CN 200410022425 A CN200410022425 A CN 200410022425A CN 1243691 C CN1243691 C CN 1243691C
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Abstract
The present invention relates to a method for preparing a barium titanate powder body which uses metatitanic acid as titanium element sources. The present invention comprises the steps: (1) sodium hydroxide and metatitanic acid react for 2.5 to 5 hours under a melting condition, and thus, the metatitanic acid is changed into sodium titanate with solubility in acid; titanic acid is obtained by water washing; (2) the titanic acid is added to oxalic acid to stir, and titanium oxalate acid solution is formed in a pH value range of 1 to 3; (3) the titanium oxalate acid solution and barium chloride solution react, the hydrating precipitate of barium titanate oxalate acid is formed, the precipitate is separated from the solution, washed in water and baked, and the baking temperature is controlled to 110 to 130 DEG C; (4) heat preservation is carried out for the hydrating precipitate of barium titanate oxalate acid which is obtained in step (3) at 850 to 1100 DEG C for 3 to 6 hours, and thus, the precipitate is completely decomposed in a hot mode to obtain the barium titanate powder.
Description
Technical field
The invention belongs to the preparation field of electronic powder material, particularly a kind of is the preparation method of the barium titanate superfine powder in titanium elements source with the metatitanic acid.
The background skill originally
Barium titanate BaTiO
3Be semiconductive ceramic---the base mateiral of positive temperature coefficient temperature sensing material PTC.Along with of the continuous increase of each manufacturing field to the ptc material demand, to the demand of its preparation raw material barium titanate, especially to the demand of " high-purity, ultra-fine, complete tetragonal structure " barium titanate especially in continuous increase.
The Chinese invention patent application discloses a kind of method for preparing tetragonal nanoparticles of barium titanate for No. 02123922.3, this method is after the aqueous solution with titanyl nitrate solution and nitrate of baryta, citric acid and ammonium nitrate mixes in proportion, heating evaporation is the colloid thing, and nano level white tetra phase barium titanate powder is prepared in ignition at a lower temperature.In No. 02135361.1, Chinese invention patent application, the another kind of method for preparing barium carbonate powder is then disclosed, the key problem in technology of this method is: titanium tetrachloride and bariumchloride or hydrated barta as main raw material, are made the precursor slurry earlier, make barium carbonate powder through hydro-thermal reaction.In No. 01131782.5, Chinese invention patent application, a kind of manufacture method of barium carbonate powder is also disclosed, this method is carried out purifying to barium salt, titanium salt respectively, make that barium salt, titanium salt behind the purifying is mixed with oxalic acid solution, coprecipitation reaction, separate, washing, removal of impurities, drying, thermal treatment obtain barium carbonate powder.Above-mentioned multiple preparation method's titanium elements source all is raw materials such as titanium tetrachloride that higher, the effective titanium content of price is lower, a large amount of liquids and gases pollutant emissions are arranged, for this reason, be necessary to study new barium titanate powder preparation, when improving the quality of products, reduce cost and eliminate environmental pollution.
Summary of the invention
The method for preparing barium carbonate powder that to the purpose of this invention is to provide a kind of metatitanic acid with cheapness be the titanium source.
Preparation method of the present invention carries out according to the following steps: (1), under melting condition, reacted 2.5～5 hours with caustic soda and metatitanic acid, metatitanic acid is changed into have acid soluble positive sodium titanate, obtain positive metatitanic acid through washing again;
(2), in positive metatitanic acid, add oxalic acid and stir formation titanium oxyoxalate acid solution in pH value 1～3 scope;
(3), this titanium oxyoxalate acid solution and barium chloride solution are reacted, form titanium oxyoxalate acid barium hydration precipitation, should precipitate and from solution, separate and impose washing, dry processing, bake out temperature is controlled between 110 ℃～130 ℃;
(4), make titanium oxyoxalate acid barium hydration that previous step obtains suddenly be deposited in 850 ℃～1100 ℃ temperature ranges insulation 3～6 hours, make it complete thermolysis, obtain barium carbonate powder.
One of creative contribution of the present invention is step (1), promptly select for use metatitanic acid as the titanium source, and with caustic soda it is changed under molten state can be by the positive metatitanic acid of oxalic acid dissolved (temperature during molten state be usually at 500 ℃～700 ℃), thereby solved higher, the effective titanium content of price that raw materials such as using titanium tetrachloride brings lower, problem such as a large amount of liquids and gases pollutant emissions arranged.Concrete steps can be (following consumption are weight part): get 1 part of metatitanic acid (determine with mud scale, with TiO
2Weight for stoichiometric equation), caustic soda is 2～5 parts, allow the two under molten state, react 2.5～5 hours, just can obtain positive sodium titanate, after this, wash more than 11 times with pure water (deionized water or distilled water) to the positive sodium titanate of gained, the bath water amount is generally 2～5 times (water consumption also can be bigger) of positive sodium titanate volume, thereby obtains the titanic Acid precipitation.
In step of the present invention (2), add oxalic acid in the titanic Acid precipitation and add pure water (deionized water or distilled water), add oxalic acid consumption can be TiO in the positive metatitanic acid
22.3～2.7 times (weight ratios) of content, the pure water amount is generally 2～5 times of titanic Acid precipitation volume, through stirring the oxalic acid and the titanic Acid precipitation that are added is fully reacted, and regulates pH value with ammoniacal liquor, makes pH value reach 1～3, thereby forms the titanium oxyoxalate acid solution.
In step of the present invention (3), be that 1～3 titanium oxyoxalate acid solution and barium chloride solution carry out precipitin reaction with pH value, form titanium oxyoxalate acid barium hydration precipitation.The consumption of bariumchloride can be TiO in the positive metatitanic acid
22.4～2.7 times (weight ratios) of content.After reaction is finished, can use pure water (deionized water or distilled water) to gained titanium oxyoxalate acid barium hydration washing of precipitate more than 11 times, the bath water amount is generally 2～5 times (water consumption also can be bigger) of titanium oxyoxalate acid barium hydration precipitation volume, the titanium oxyoxalate that obtains cleaning acid barium hydration precipitation.After this, the titanium oxyoxalate acid barium hydration of cleaning is deposited under 110 ℃～130 ℃ temperature dries.
In step of the present invention (4), the titanium oxyoxalate acid barium hydration precipitation heating to obtaining after the oven dry makes it to be warming up to 850 ℃～1100 ℃, after allowing the hydration of titanium oxyoxalate acid barium be deposited in to carry out thermolysis under 850 ℃～1100 ℃ high temperature, obtains barium carbonate powder.Generally, allow the hydration of titanium oxyoxalate acid barium be deposited in 850 ℃～1100 ℃ the temperature range insulation 3～6 hours, can finish above-mentioned thermolysis.The purpose of drying under 110 ℃～130 ℃ temperature is in order to remove a large amount of free waters, guarantee microscopic uniformity, the purpose that is incubated 3～6 hours under 850 ℃～1100 ℃ high temperature is for oxalate is decomposed fully, to guarantee the high purity of product, if temperature is too high or soaking time is long, the granularity of powder is increased.
Another creative contribution of the present invention promptly is in step (2) and step (3), above-mentioned steps (2) and step (3) have been broken the process sequence that traditional titanium tetrachloride is made the oxalic acid liquid phase method in titanium source, adopted make titanium ion and oxalic acid form complex compound earlier after, the step of carrying out precipitin reaction again with bariumchloride.Detect proof, although this changes and makes carry out thermolysis under 850 ℃～1100 ℃ high temperature, the still very little (mean particle size≤300nm) of the mean particle size of the barium carbonate powder that is obtained.
In the present invention, after above-mentioned steps (4) was handled, the barium carbonate powder that the obtains loose shape that is white in color did not need to carry out mechanical disintegration again, can directly obtain barium titanate superfine powder (mean particle size≤300nm).
Barium titanate powder preparation of the present invention has following positively effect: overcome the shortcoming that traditional titanium tetrachloride is done the cost height of the Oxalic Acid Method in titanium source, a large amount of liquids and gases pollutant emissions 1.; 2. adopt alkali fusion to make metatitanic acid be converted into positive metatitanic acid, experimental results show that, positive metatitanic acid is the same with titanium tetrachloride, also the titanium oxyoxalate acid solution can be formed with the oxalic acid complex reaction and under the condition of pH value 1～3, and the caustic soda soln that washing is come out can recycle after concentrating evaporate to dryness, helps preventing the pollution and the cost that economizes in raw materials; 3. broken traditional titanium tetrachloride and made the process sequence of the oxalic acid liquid phase method in titanium source, adopted make titanium ion and oxalic acid form complex compound earlier after, the step of carrying out precipitin reaction again with bariumchloride has guaranteed the superfine granularity of the barium carbonate powder that makes; 4. preparation technology is better than the Oxalic Acid Method that traditional titanium tetrachloride is done the titanium source, can save operation, place and the equipment of preparing the liquid titanium tetrachloride of high strong acid and high risk under the low temperature.Through X-ray diffraction analysis, the crystal formation of the prepared product of the inventive method is a tetragonal structure, and through scanning electron microscope analysis, its mean particle size≤300nm through chemical analysis, proves that its purity can reach 99.7%, and the Ba/Ti mol ratio is 0.997～1.003.
Content of the present invention further illustrates with the following Examples, but content of the present invention is not limited only to content related among the embodiment.
Description of drawings
Fig. 1 is the X-ray diffractogram with made barium carbonate powder among the embodiment 1.
Fig. 2 is with made barium carbonate powder electron scanning micrograph among the embodiment 1.
Embodiment
Embodiment 1: the barium titanate powder preparation in the present embodiment carries out according to the following steps:
(1), under melting condition, reacted 3 hours, metatitanic acid is changed into have acid soluble positive sodium titanate, obtain positive metatitanic acid through washing again with caustic soda and metatitanic acid.In this step, weigh in the balance to get and contain TiO
2Stoichiometry is the metatitanic acid of 100 grams, adds caustic soda 250 grams, and fusion 3 hours obtains the positive sodium titanate solid of vesicular (this moment, its volume was roughly 300 milliliters).With positive sodium titanate washing 13 times, the titanic sour water that obtains to clean closes precipitation with 1000 milliliters of distilled water.
(2), in positive metatitanic acid, add oxalic acid and stir formation titanium oxyoxalate acid solution under the condition of pH value 1.5.In this step, 230 gram oxalic acid are added in the titanic Acid precipitation of cleaning (this moment, its volume was roughly 600 milliliters), add 2000 ml pure waters, constantly stir, regulate pH value with ammoniacal liquor, under the condition of pH value 1.5, form the titanium oxyoxalate acid solution.
(3), this titanium oxyoxalate acid solution and barium chloride solution are reacted, form titanium oxyoxalate acid barium hydration precipitation, should precipitate and from solution, separate and impose washing, dry processing, bake out temperature is controlled at about 120 ℃.In this step, be that 1.5 titanium oxyoxalate acid solution and barium chloride solution carry out precipitin reaction with pH value, form titanium oxyoxalate acid barium hydration precipitation.It is that to join pH value behind 10% the aqueous solution be in 1.5 the titanium oxyoxalate acid solution that 260 gram bariumchlorides are formulated as concentration, under agitation carries out precipitin reaction, generates titanium oxyoxalate acid barium hydration precipitation.3 times pure water using titanium oxyoxalate acid barium hydration precipitation volume again is to gained titanium oxyoxalate acid barium hydration washing of precipitate 15 times, obtain cleaning titanium oxyoxalate acid barium hydration precipitation.After this, again this titanium oxyoxalate acid barium hydration precipitation is inserted in the loft drier, under the temperature about 120 ℃, dried.
(4), the titanium oxyoxalate acid barium hydration that previous step is obtained suddenly is deposited under 900 ℃ of high temperature and carries out thermolysis, the acquisition barium carbonate powder.In this step, titanium oxyoxalate acid barium hydration after the oven dry is deposited in carries out thermolysis in the chamber type electric resistance furnace, be about to this titanium oxyoxalate acid barium hydration precipitation and be warming up to 900 ℃ and insulation 3.5 hours in this temperature range, make titanium oxyoxalate acid barium at high temperature carry out obtaining after the thermolysis barium carbonate powder of white loose.
Main chemical reactions formula among the embodiment 1 has:
The every Measurement results of barium titanate that present embodiment is obtained is as follows:
1., crystal formation: the X-ray diffraction analysis, the powder tetragonal structure barium titanate that obtains, X-ray diffraction analysis chart and data are seen accompanying drawing 1.
2., chemical composition analysis: chemical composition analysis data such as following table 1.
The main component index of the barium titanate of this prepared of table 1
| BaTiO 3 | Weight (TiO 2)％ | Barium/titanium is than (mole) |
| Embodiment 1 | 99.77 | 0.998 |
3., granularity: use scanning electron microscope test, the barium titanate mean particle size that is obtained is 277nm, and is identical with external product, and size-grade distribution is seen accompanying drawing 2 in the scope less than 400nm.
Embodiment 2: the barium titanate powder preparation in the present embodiment carries out according to the following steps:
(1), under melting condition, reacted 4.5 hours, metatitanic acid is changed into have acid soluble positive sodium titanate, obtain positive metatitanic acid through washing again with caustic soda and metatitanic acid.In this step, weigh in the balance to get and contain TiO
2Stoichiometry is the metatitanic acid of 100 grams, adds caustic soda 250 grams, and fusion 4.5 hours obtains the positive sodium titanate solid of vesicular (this moment, its volume was roughly 300 milliliters).With positive sodium titanate washing 13 times, the titanic sour water that obtains to clean closes precipitation with 1000 milliliters of distilled water.
(2), in positive metatitanic acid, add oxalic acid and stir formation titanium oxyoxalate acid solution under the condition of pH value 2.0.In this step, 232 gram oxalic acid are added in the titanic Acid precipitation of cleaning (this moment, its volume was roughly 600 milliliters), add 2000 ml pure waters, constantly stir, regulate pH value with ammoniacal liquor, under the condition of pH value 2.0, form the titanium oxyoxalate acid solution.
(3), this titanium oxyoxalate acid solution and barium chloride solution are reacted, form titanium oxyoxalate acid barium hydration precipitation, should precipitate and from solution, separate and impose washing, dry processing, bake out temperature is controlled at about 120 ℃.In this step, be that 2.0 titanium oxyoxalate acid solution and barium chloride solution carry out precipitin reaction with pH value, form titanium oxyoxalate acid barium hydration precipitation.It is that to join pH value behind 10% the aqueous solution be in 2.0 the titanium oxyoxalate acid solution that 262 gram bariumchlorides are formulated as concentration, under agitation carries out precipitin reaction, generates titanium oxyoxalate acid barium hydration precipitation.3 times pure water using titanium oxyoxalate acid barium hydration precipitation volume again is to gained titanium oxyoxalate acid barium hydration washing of precipitate 15 times, obtain cleaning titanium oxyoxalate acid barium hydration precipitation.After this, again this titanium oxyoxalate acid barium hydration precipitation is inserted in the loft drier, under the temperature about 120 ℃, dried.
(4), the titanium oxyoxalate acid barium hydration that previous step is obtained suddenly is deposited under 1050 ℃ of high temperature and carries out thermolysis, the acquisition barium carbonate powder.In this step, titanium oxyoxalate acid barium hydration after the oven dry is deposited in carries out thermolysis in the chamber type electric resistance furnace, be about to this titanium oxyoxalate acid barium hydration precipitation and be warming up to 1050 ℃ and insulation 4.5 hours in this temperature range, make titanium oxyoxalate acid barium at high temperature carry out obtaining after the thermolysis barium carbonate powder of white loose.
Embodiment 3: the barium titanate powder preparation in the present embodiment carries out according to the following steps:
(1), under melting condition, reacted 3.5 hours, metatitanic acid is changed into have acid soluble positive sodium titanate, obtain positive metatitanic acid through washing again with caustic soda and metatitanic acid.In this step, weigh in the balance to get and contain TiO
2Stoichiometry is the metatitanic acid of 100 grams, adds caustic soda 250 grams, and fusion 3.5 hours obtains the positive sodium titanate solid of vesicular (this moment, its volume was roughly 300 milliliters).With positive sodium titanate washing 13 times, the titanic sour water that obtains to clean closes precipitation with 1000 milliliters of distilled water.
(2), in positive metatitanic acid, add oxalic acid and stir formation titanium oxyoxalate acid solution under the condition of pH value 2.5.In this step, 250 gram oxalic acid are added in the titanic Acid precipitation of cleaning (this moment, its volume was roughly 600 milliliters), add 2000 ml pure waters, constantly stir, regulate pH value with ammoniacal liquor, under the condition of pH value 2.5, form the titanium oxyoxalate acid solution.
(3), this titanium oxyoxalate acid solution and barium chloride solution are reacted, form titanium oxyoxalate acid barium hydration precipitation, should precipitate and from solution, separate and impose washing, dry processing, bake out temperature is controlled at about 120 ℃.In this step, be that 2.5 titanium oxyoxalate acid solution and barium chloride solution carry out precipitin reaction with pH value, form titanium oxyoxalate acid barium hydration precipitation.It is that to join pH value behind 10% the aqueous solution be in 2.5 the titanium oxyoxalate acid solution that 250 gram bariumchlorides are formulated as concentration, under agitation carries out precipitin reaction, generates titanium oxyoxalate acid barium hydration precipitation.3 times pure water using titanium oxyoxalate acid barium hydration precipitation volume again is to gained titanium oxyoxalate acid barium hydration washing of precipitate 15 times, obtain cleaning titanium oxyoxalate acid barium hydration precipitation.After this, again this titanium oxyoxalate acid barium hydration precipitation is inserted in the loft drier, under the temperature about 120 ℃, dried.
(4), the titanium oxyoxalate acid barium hydration that previous step is obtained suddenly is deposited under 1000 ℃ of high temperature and carries out thermolysis, the acquisition barium carbonate powder.In this step, titanium oxyoxalate acid barium hydration after the oven dry is deposited in carries out thermolysis in the chamber type electric resistance furnace, be about to this titanium oxyoxalate acid barium hydration precipitation and be warming up to 1000 ℃ and insulation 4 hours in this temperature range, make titanium oxyoxalate acid barium at high temperature carry out obtaining after the thermolysis barium carbonate powder of white loose.
Embodiment 4: the barium titanate powder preparation in the present embodiment carries out according to the following steps:
(1), under melting condition, reacted 4 hours, metatitanic acid is changed into have acid soluble positive sodium titanate, obtain positive metatitanic acid through washing again with caustic soda and metatitanic acid.In this step, weigh in the balance to get and contain TiO
2Stoichiometry is the metatitanic acid of 100 grams, adds caustic soda 250 grams, and fusion 4 hours obtains the positive sodium titanate solid of vesicular (this moment, its volume was roughly 300 milliliters).With positive sodium titanate washing 13 times, the titanic sour water that obtains to clean closes precipitation with 1000 milliliters of distilled water.
(2), in positive metatitanic acid, add oxalic acid and stir formation titanium oxyoxalate acid solution under the condition of pH value 2.5.In this step, 255 gram oxalic acid are added in the titanic Acid precipitation of cleaning (this moment, its volume was roughly 600 milliliters), add 2000 ml pure waters, constantly stir, regulate pH value with ammoniacal liquor, under the condition of pH value 2.5, form the titanium oxyoxalate acid solution.
(3), this titanium oxyoxalate acid solution and barium chloride solution are reacted, form titanium oxyoxalate acid barium hydration precipitation, should precipitate and from solution, separate and impose washing, dry processing, bake out temperature is controlled at about 120 ℃.In this step, be that 2.5 titanium oxyoxalate acid solution and barium chloride solution carry out precipitin reaction with pH value, form titanium oxyoxalate acid barium hydration precipitation.It is that to join pH value behind 10% the aqueous solution be in 2.5 the titanium oxyoxalate acid solution that 255 gram bariumchlorides are formulated as concentration, under agitation carries out precipitin reaction, generates titanium oxyoxalate acid barium hydration precipitation.3 times pure water using titanium oxyoxalate acid barium hydration precipitation volume again is to gained titanium oxyoxalate acid barium hydration washing of precipitate 15 times, obtain cleaning titanium oxyoxalate acid barium hydration precipitation.After this, again this titanium oxyoxalate acid barium hydration precipitation is inserted in the loft drier, under the temperature about 120 ℃, dried.
(4), the titanium oxyoxalate acid barium hydration that previous step is obtained suddenly is deposited under 960 ℃ of high temperature and carries out thermolysis, the acquisition barium carbonate powder.In this step, titanium oxyoxalate acid barium hydration after the oven dry is deposited in carries out thermolysis in the chamber type electric resistance furnace, be about to this titanium oxyoxalate acid barium hydration precipitation and be warming up to 960 ℃ and insulation 5 hours in this temperature range, make titanium oxyoxalate acid barium at high temperature carry out obtaining after the thermolysis barium carbonate powder of white loose.
Claims (1)
1, a kind of is the preparing barium titanate powder in titanium elements source with the metatitanic acid, it is characterized in that carrying out according to the following steps:
(1), under melting condition, reacted 2.5～5 hours, metatitanic acid is changed into have acid soluble positive sodium titanate, obtain positive metatitanic acid through washing again with caustic soda and metatitanic acid;
(2), in positive metatitanic acid, add oxalic acid and stir formation titanium oxyoxalate acid solution in pH value 1～3 scope;
(3), this titanium oxyoxalate acid solution and barium chloride solution are reacted, form titanium oxyoxalate acid barium hydration precipitation, should precipitate and from solution, separate and impose washing, dry processing, bake out temperature is controlled between 110 ℃～130 ℃;
(4), make titanium oxyoxalate acid barium hydration that previous step obtains suddenly be deposited in 850 ℃～1100 ℃ temperature ranges insulation 3～6 hours, make it complete thermolysis, obtain barium carbonate powder.
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| CN109879311B (en) * | 2019-03-20 | 2021-04-20 | 成都理工大学 | Method for preparing titanium suboxide by reducing titanium-containing complex at normal temperature |
| CN115477324B (en) * | 2022-09-06 | 2023-10-03 | 东南大学 | Preparation method of tetragonal phase nano barium titanate |
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