CN85101148A - The preparation method of fibrous alkali metal titanate - Google Patents
The preparation method of fibrous alkali metal titanate Download PDFInfo
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- CN85101148A CN85101148A CN 85101148 CN85101148A CN85101148A CN 85101148 A CN85101148 A CN 85101148A CN 85101148 CN85101148 CN 85101148 CN 85101148 A CN85101148 A CN 85101148A CN 85101148 A CN85101148 A CN 85101148A
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Abstract
The method for preparing a kind of fibrous alkali metal titanate comprises the slurry of dry titanium-containing compound and oxygen containing alkali metal compound.Bake the dry mixture of crossing and pulverize the sinter that generates.
Description
The invention relates to a method for preparing fibrous alkali metal titanate, particularly contain the method for preparing fibrous alkali metal titanate the oxonium base metallic compound from a kind of titanium-containing compound and about one.
Fibrous alkali metal titanate is used as the strongthener of plastics, the barrier film of abrasive material, filtering material, battery, pigment, thermal insulation material or the like.
The method of many certain fibrous alkali metal titanates of preparation had been proposed.For example, molten roasting method, scorification, hydrothermal method, flux method and improved scorification are wherein arranged.In arbitrary method, contain the oxonium base metallic compound as starting material with titanyl compound and alkalescence usually.
At present, wish with the surrogate of a kind of fibrous alkali metal titanate as asbestos.Yet the aspect ratio of the fibrous alkali metal titanate that can buy (staple length/Fibre diameter) is littler than asbestos at present, in fact can not use.Japanese patent gazette NO.27,264/1967(Japanese Examined Patent Publication NO.27,264/1967) announce, as the aqueous titanium dioxide that has of titanium source use.Anatase octahedrite prepares pigment with sulphate process, a kind of TiO of containing that electronic material or catalyzer obtain
2Product, the rutile ore of purified anatase pigment, pulverizing and commercially available ilmenite.Alkali-metal oxyhydroxide, alkali-metal carbonate etc. also disclosed as a kind of oxonium base metallic compound that contains of alkalescence.Above-mentioned Japanese patent gazette NO27,264/1967(Japanese Publicatin NO.27,264/1967) also relates under 200 to 1150 ℃ of temperature, prepare a kind of fibrous alkali metal titanate with the method that alkalescence contains a kind of non-liquid mixture of oxonium base metallic compound composition with baking above-mentioned titanium source.Mainly to contain diameter be 0.005 to 0.1 μ m in preparation, and length is at least under the situation of alkali metal titanate of colloid type compound of ten times of its diameters, bakes said mixture for 200 to 850 ℃ in temperature.Mainly to contain diameter is 0.1 to 0.6 μ m when preparation, when length is the alkali metal titanate of pigment style compound of 10～100 times of its diameters, at 850 to 975 ℃ of baked mixts of temperature.Under the situation of 975 to 1150 ℃ of baked mixts of temperature, it is 0.6 to 33.0 μ m that the alkali metal titanate that obtains mainly contains diameter, and length is the compound of the heat insulation-type of 100 to 1000 times of its diameters.In addition, this publication adds a kind of alkali metal halide in initial non-liquid mixture before also being disclosed in and baking.
The fibrous alkali metal titanate that obtains in aforesaid method is difficult to separate from the fibrous sinter that bakes formation, and owing to fibre breakage in crushing process, the fibrous alkali metal titanate that obtains has only the length of 10 to 20 μ m and one about 50 aspect ratio.Therefore, the performance of the fibrous titanate that obtains does not reach requirement, and application will be restricted.
The objective of the invention is, provide a preparation to be easy to separate, again the method for a kind of fibrous alkali metal titanate of easy fracture not in crushing process from the fibrous sinter that bakes generation.
Another object of the present invention is to provide a preparation to have the big aspect ratio and the method for high-intensity fibrous alkali metal titanate.
As can be seen, the above-mentioned and other purpose of the present invention is obvious from following narration.
The method of a kind of fibrous alkali metal titanate of preparation provided by the invention comprises: the dry slurry of being made up of certain titanium-containing compound and certain oxygen containing alkali metal compound (slurry) bakes the dry mixture of crossing and pulverizes the sinter that generates.
Among the present invention, titanium-containing compound refers to that those essence contain TiO
2The compound that exists or do not exist with slurry form with slurry form.The example of useful titanium-containing compound has the hydroxide slurry (wet cake) of titanyl compound, rutile ore, titanium, moisture titanium dioxide or the like.These compounds are preferably to exist with the fine particle form.Desirable titanyl compound example is a kind of fine particle of anatase octahedrite.The example of desirable rutile ore is a kind of fine particle that obtains with the method that particle collides under high speed mutually.Be commonly referred to " injection-sized particles (" jet-puiver-ized particle ").These titanium-containing compounds preferably have 200 to 425 purpose granularities.
The example of the hydroxide slurry of desirable titanium (wet cake) is the industrial intermediate product that obtains in the titanyl compound process for preparing with sulfuric acid process.Heating titanium ore or titanium ore slag in sulfuric acid, extracting and the titanyl sulfate (titanyl sulfate) of purifying and generating, the heating hydrolysis titanyl sulfate is bleached and is cleaned hydrolysate when needed and just obtains this slurry.
This slurry has following composition approx.
TiO(OH)
240.4 calculate by weight to 49.0%()
(33 press TiO to 40%
2Weight calculate)
H
2SO
42.0 to 3.2% (calculating by weight)
(6.1 to 9.8% with TiO
2Weight be that benchmark calculates)
H
2O 47.8 calculates by weight to 57.6%()
The method of the most handy adding water is adjusted to slurry and contains 10% to 35% by weight TiO
2, but be not limited to this.
In the present invention, the oxonium base metallic compound that contains of use is that those generate M when baking
2O(M is a basic metal) compound.Compound can be slurry form or non-slurry form.This compounds comprises the oxide compound of potassium, sodium, caesium and rubidium, oxyhydroxide, carbonate, acid carbonate, oxalate and nitrate.K is for example arranged
2O, KOH, K
2CO
3, KHCO
3, K
2C
2O
4, KNO
3, Na
2O, NaOH, Na
2CO
3, NaHCO
3, Na
2C
2O
4, NaNO
3, Cs
2O, CsOH, Cs
2CO
3, CsHCO
3, Cs
2C
4O
4, CsNO
3, Rb
2O, RbOH, Rb
2CO
3, RbHCO
3, Rb
2C
2O
4, RbNO
3Or the like.
According to the present invention, titanium-containing compound and contain the oxonium base metallic compound and be made into slurry, this slurry is dried and obtains particle, permission mixes the starting material of two kinds of slurry forms, also allow water is added in the starting material of two kinds of non-slurry forms, perhaps a kind of raw material of non-slurry form is added in a kind of raw material of slurry form.In addition, in needs, can be added to water in the slurry of generation and go.Slurry heating method drying.But spraying drying preferably.
When spraying drying, in the particle that obtains, contain the oxonium base metallic compound equably, be attached to the surface of titanium-containing compound with fine powder powdery attitude.When this particle is baked, contain the oxonium base metallic compound with a very high speed of response diffusion be penetrated into TiO
2In, to produce a kind of fibrous alkali metal titanate with high aspect ratio.Slurry preferably contains by TiO
210% to 45% the titanium-containing compound that weight is calculated, slurry is preferably under about 50 to 250 ℃ temperature and carries out drying.The dry particle grain size of crossing is decided by the exsiccant temperature, the concentration of slurry.When spraying drying, be decided by that also the speed of feed and nozzle are still disc type rotary-type (disc-revolution) of dish-type (disc-shape).About 50 to the 5500 μ m of particle diameter are for well.
Titanium-containing compound and the ratio TiO that contains the oxonium base metallic compound
2/ M
2The mole ratios of O represents, with 3 to 3.5 for well, but is not limited to this.Can add a spot of Repone K as a kind of supplementary additive.Can bake the dry raw mix of crossing by original form, but preferably be pressed into shaped product for the reactivity worth of improving them with higher density.In this case, for a good forming property is arranged, preferably in mixture, add a spot of water, organic binder bond or surfactant.Mixture is shaped under a suitable pressure, and pressure normally 20 arrives 300kg/cm
2, preferably 50 arrive 150kg/cm
2
The dry mixture of crossing can bake in a very wide temperature range, but to bake in 900 to 1300 ℃ temperature range to good, bakes better in 1000 to 1200 ℃ temperature range.Bake the time with about 15 minutes to 6 hours for well, be more preferably about 30 minutes to 3 hours.In addition, arrive enough length in order to make fiber growth, it is reasonable cooling off the alkali metal titanate that bakes generation gradually.Cooling can be carried out with the reduction method of temperature in a very wide scope gradually, but normally carries out under 900 to 950 ℃ temperature.In addition, utilize and to bake once more or to repeat at least after the cooling gradually to comprise for twice and bake and the refrigerative process fiber that can obtain to have high aspect ratio gradually.
Can obtain a kind of fibrous sinter that is mainly by above-mentioned reaction.In the present invention, pulverize this sinter and just prepare a kind of fibrous alkali metal titanate with high aspect ratio.
The fibrous material that obtains is added in the water, with DISPER agitator or similarly agitator pulverizing.Fiberous material is preferably in to be placed in the water one hour at least, made it become tight.Various known devices all can be used for pulverizing, and the material of the method pulverized fiber shape that the most handy material collides under high speed mutually (is called " injection-comminuting method " to this method hereinafter.To mainly contain the suspension filtered of the fiber of pulverizing, dry filter thing (filtrates) just generates the fibrous alkali metal titanate of wishing.
In the present invention, when original slurry during, contain oxonium base metallic compound and TiO when baking by spraying drying
2React equably with high speed of response.Can pulverize the alkali metal titanate sinter that generates at an easy rate, make product hope, that have high aspect ratio.
Fibrous alkali metal titanate of the present invention is the compound of the chemical formulation below a kind of usefulness:
M
2O·nTiO
2
M is a basic metal in the formula, and n is a real number of 2 to 8, or the mixture of these compounds.Above-mentioned titanate has the staple length of Fibre diameter and best 50 to the 300 μ m of best 0.1 to 1 μ m.
Present invention is described with reference to embodiment and comparative example below, in these examples, unless do explanation in addition, all is by weight calculation for % number.
Embodiment 1
The hydroxide slurry (TiO of a titanium
229.9%, H
2SO
44.17%) puts into a container that high speed agitator is housed.In addition, in and slurry in H
2SO
4With react, add potassium hydroxide again and make TiO
2/ K
2The mole ratio of O equals 3.3 and make the mixture thorough mixing.The slurry that generates is put into baking oven to spend the night.The dry mixture of crossing is pulverized subtly.The mould that mixture is 60mm with a diameter is at 200kg/cm
2Pressure be shaped down.The mixture that is shaped was put into a retort furnace, 1100 ℃ of heating 7 hours.The product that baked is spent the night by rough the pulverizing in the back immersion water.Remove by filter water, filtrate is washed, drying just obtains a kind of fibrous potassium titanate.The table I has shown the productive rate and the fiber properties of this fibrous potassium titanate.
Embodiment 2
Put into retort furnace according to the shaping mixt that obtains with routine I same procedure, 1100 ℃ of heating 4 hours.Then with 20 ℃/time speed mixture be cooled to gradually 950 ℃ make the reaction finish.By with routine I in same method pulverize the product that baked and just obtain a kind of fibrous potassium titanate.The table I has provided the productive rate and the fiber properties of this potassium titanate.
Embodiment 3
Except replacing the potassium hydroxide, by preparing a kind of fibrous titanate with the same method of routine I with salt of wormwood (one-level chemical reagent).Table 1 is listed the productive rate of this fibrous potassium titanate and fiber with property.
Embodiment 4
Salt of wormwood (one-level chemical reagent) is added in the hydroxide slurry of the titanium identical, for neutralizing acid with react and make TiO with example 1
2/ K
2The mole ratios of O equals 3.5.Except using above mixture, prepare a kind of fibrous potassium titanate by the method identical with example 1.Table 1 has shown the productive rate and the fiber properties of this fibrous potassium titanate.
Comparative example 1
The ammoniacal liquor of finishing the neutralizing effect desired number is added in the hydroxide slurry of the titanium identical, adds salt of wormwood again and make TiO in order to react with example 1
2/ K
2The mole ratios of O equals 3.3.Except using above mixture, prepare a kind of fibrous potassium titanate by the method identical with example 1.Table 1 has shown the productive rate and the fiber properties of this fibrous potassium titanate.
Comparative example 2
To obtain a kind of aqueous titanium dioxide according in the same method of comparative example 1 and that the hydroxide slurry of the titanium of crossing filters, a baking oven is put in washing again is dry, and add salt of wormwood (one-level chemical reagent) again and make TiO
2/ K
2The mole ratios of O equals 3.3.Utilize a mixing tank to make this mixture thorough mixing.Use the mould of a diameter 60mm again, at 200kg/cm
2Pressure be shaped down.The mixture that is shaped is put into a retort furnace, 1100 ℃ of heating 7 hours.The product that baked is pulverized the back roughly and is immersed in the water and spend the night, and removes by filter water, and filtrate is washed, just obtain a kind of fibrous potassium titanate after the drying.Table 1 has shown the productive rate and the fiber properties of this fibrous potassium titanate.
Comparative example 3
With TiO
2Be to calculate benchmark, vitriolate of tartar (one-level chemical reagent) is added the anatase octahedrite of buying in market (a kind of product of Teikoku Kako company limited), and to make the weight percentage of vitriolate of tartar be 25%.Add salt of wormwood (one-level chemical reagent) again and make TiO for reacting
2/ K
2The mole ratios of O equals 3.3.Except using above mixture, prepare a kind of fibrous potassium titanate by similarly to Example 1 method.Table 1 has shown the productive rate and the fiber properties of this fibrous potassium titanate.
(annotating 1) A: potassium tetratitanate (potassium tetratitanate)
B: six potassium titanates (potassium hexatitanate)
Embodiment 5
The rutile powder of pulverizing and salt of wormwood is added to makes TiO in the water
2/ K
2The mole ratios of O equals 3.Rutile powder passes through
#350 sieves, its fundamental analysis are 97.5%TiO
2, 0.2%SiO
2, 0.25%Al
2O
3, 0.15%Fe
2O
3, 0.5%ZrO
2With the dry slurry that generates of a spray-dryer (OC-16 type, a kind of product of Ogawara Kakoki company limited), obtain having the particulate that the drying of good fluidity is crossed.Particulate is with the mould of a diameter 60mm, at 200kg/cm
2Pressure is shaped down.Product after the shaping was put into an electric furnace, 1100 ℃ of heating 7 hours.The product that baked is pulverized roughly in the back immersion water and is spent the night.Remove with filtration method and to anhydrate, with the filtrate drying.The product pulverizing of drying being crossed with an injection-shredding unit (PJM-100 type, a kind of product of Nchon Neumatic Industrial Co., Ltd) just obtains a kind of fibrous potassium titanate.Table 2 has provided the productive rate and the fiber properties of this fibrous potassium titanate.
Embodiment 6
A kind of hydroxide slurry (TiO of titanium
229.9%, H
2SO
44.17%) is put in the container that high speed agitator is housed, for the H in the material material that neutralizes
2SO
4Add potassium hydroxide again with reacting, make TiO
3/ K
2The O mole ratios equals 3, and mixture is by thorough mixing, and the slurry of generation is by just obtaining the exsiccant particulate with the same method spraying drying of example 5.Particulate is with the mould of a diameter 60mm, at 100kg/cm
2Pressure is shaped down.The product that was shaped is 1100 ℃ of heating 4 hours, then by 20 ℃/time speed be cooled to 950 ℃ gradually and finish reaction.Product is pulverized the back roughly and is immersed in the water, and then puts into a hot water.With DISPER agitator crushed products, the material of filter fiber shape, washing, dry filter thing just obtain a kind of fibrous potassium titanate again, the results are shown in table 2.
Embodiment 7
The titanyl compound of having bought on the market (anatase octahedrite) and salt of wormwood added together make TiO in the entry
2/ K
2The O mole ratios equals 3.The slurry that generates is by just obtaining the exsiccant particulate with the same method spraying drying of example 5.Particulate is at 100kg/cm
2Pressure be shaped down and prepare a diameter 60mm, the shaped product of high 30mm, the product of shaping are put into a retort furnace 1100 ℃ of heating 7 hours.Except using top baking the product, by preparing a kind of fibrous potassium titanate with the same method of example 6.The results are shown in table 2.
Claims (11)
1, a kind of method for preparing fibrous alkali metal titanate, this method comprises, the slurry of dry a kind of titanium-containing compound and a kind of oxygen containing alkali metal compound bakes the dry mixture of crossing and pulverizes the sinter that generates.
2, according to the method for claim 1 narration, wherein, titanium-containing compound and oxygenatedchemicals are pressed TiO
2/ M
2O(M is a basic metal) mole ratio equals 3 to 3.5 mode and mixes.
3, according to the method for claim 1 narration, wherein, press TiO
2Calculate, slurry comprises 10% to 45%(weight) titanium-containing compound.
4, according to the method for claim 1 narration, wherein, oxygen containing alkali metal compound is from comprising alkali-metal oxide compound, select at least a compound in one group of compound of oxyhydroxide and carbonate.
5, according to the method for claim 1 narration, wherein, slurry is by spraying drying.
6, according to the method for claim 1 narration, wherein, baking is to carry out under 900 to 1300 ℃ temperature.
7, according to the method for claim 1 narration, wherein, the dry mixture of crossing bakes under 900 to 1300 ℃ temperature, and the product that baked is cooled to 900 to 950 ℃ temperature gradually.
8, according to the method for claim 1 narration, wherein, the dry mixture of crossing bakes in 900 ℃ to 1300 ℃ temperature range after baking and little by little be cooled to 900 to 950 ℃ under 900 to 1300 ℃ the temperature more once more.
9, according to the method for claim 7 narration, wherein, be included in 900 to 1300 ℃ of operating process that bake and be cooled to gradually 900 to 950 ℃ and be repeated at least twice.
10, according to the method for claim 1 narration, wherein, pulverize sinter with spraying breaking method.
11, according to the method for claim 1 narration, wherein, alkali metal titanate is a kind of compound with following chemical formulation:
M is a basic metal in the formula, and n is a real number of 2 to 8, or the mixture of these compounds.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6498284A JPS60210528A (en) | 1984-03-30 | 1984-03-30 | Production of fibrous alkali metal titanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85101148A true CN85101148A (en) | 1987-01-17 |
Family
ID=13273768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101148 Pending CN85101148A (en) | 1984-03-30 | 1985-04-01 | The preparation method of fibrous alkali metal titanate |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS60210528A (en) |
| CN (1) | CN85101148A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250751B (en) * | 2007-11-30 | 2010-06-09 | 江苏大学 | Method for preparing crystal wisker of potassium hexatitanate |
| CN102259910A (en) * | 2011-06-16 | 2011-11-30 | 申偲伯 | Method for producing potassium titanate in large scale by utilizing ore-grade titanium-containing compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2835423A1 (en) * | 1978-08-12 | 1980-03-06 | Hoechst Ag | CONCRETE AND MORTAR ADDITIVES AND THEIR USE |
| JPS5637218A (en) * | 1979-11-03 | 1981-04-10 | Kyushu Refract Co Ltd | Heat-resistant fibrous substance |
-
1984
- 1984-03-30 JP JP6498284A patent/JPS60210528A/en active Granted
-
1985
- 1985-04-01 CN CN 85101148 patent/CN85101148A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250751B (en) * | 2007-11-30 | 2010-06-09 | 江苏大学 | Method for preparing crystal wisker of potassium hexatitanate |
| CN102259910A (en) * | 2011-06-16 | 2011-11-30 | 申偲伯 | Method for producing potassium titanate in large scale by utilizing ore-grade titanium-containing compound |
| CN102259910B (en) * | 2011-06-16 | 2014-03-12 | 申偲伯 | Method for producing potassium titanate in large scale by utilizing ore-grade titanium-containing compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60210528A (en) | 1985-10-23 |
| JPH0432764B2 (en) | 1992-06-01 |
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