CN102766154A - Method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method - Google Patents
Method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method Download PDFInfo
- Publication number
- CN102766154A CN102766154A CN2012102641311A CN201210264131A CN102766154A CN 102766154 A CN102766154 A CN 102766154A CN 2012102641311 A CN2012102641311 A CN 2012102641311A CN 201210264131 A CN201210264131 A CN 201210264131A CN 102766154 A CN102766154 A CN 102766154A
- Authority
- CN
- China
- Prior art keywords
- zirconium
- solvent
- organic
- gathers
- phase stabilizer
- 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
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method. The method includes proportioning zirconium oxychloride octahydrate, ligand acetyl acetone, ethyl acetoacetate or alcohol ether, precipitation separation agent C1-C5 which is straight-chain diamine or branched-chaine diamine, triethanolamine, ornithine or ammonia gas, phase stabilizer which is yttrium, calcium, magnesium or cerium chloride and the like according a certain ratio, adding solvent C1-C4 alcohol or mixture solvent thereof to sufficiently react with stirring at the temperature of 0-50 DEG C, filtering to remove hydrochloride, subjecting the obtained solution to pressure reduction and concentration at the temperature of 20-50 DEG C to obtain organic poly-zirconium precursor or silk-thrawn liquor; and obtaining high-quality zirconia crystal fibers by centrifugal silk throwing and fiber thermal treatment. Compared with the conventional zirconia fiber preparation technology, the method for preparing organic poly-zirconium precursor has the advantages of simple process, low cost, high yield, environment-friendliness, and product obtained is high in quality and the like.
Description
Technical field
The present invention relates to produce fully and organicly in the crystal of zirconium oxide fiber gather the zirconium precursor body or it gets rid of the preparation method of a liquid with organic zirconium legal system of gathering, particularly a step solvent method prepares and organicly gathers the zirconium precursor body or it gets rid of the method for a liquid.
Background technology
Fast development along with sophisticated technology progress and modern industry; Heatproof, heat-proof quality to the refractory heat-insulating fiber require also increasingly high; Traditional fiber has been difficult to life-time service under high temperature (especially surpassing 1800 ℃ oxidizing atmosphere environment), and has the big drawback of energy consumption.Zirconium white is at present unique oxide compound that has high temperature resistant, minimum thermal conductivity, minimum high temperature steam pressure and excellent performances such as acid-alkali-corrosive-resisting concurrently.Compare with other inorganic fibres, high-performance many uniquenesses, irreplaceable that Zirconium oxide fibre has, the field all has extremely important using value and bright prospects in that Aeronautics and Astronautics and ultrahigh-temperature Industrial Stoves are heat insulation etc.
Zirconium oxide fibre and goods thereof have more excellent heatproof, heat insulation, energy-saving effect than other oxide fibre.The key in promote the oxidation zirconium fiber applications paces and expansion at present, popularization field is further to simplify, improve its technology of preparing, reduce cost significantly and optimize comprehensively, to improve performance.The patent that the applicant is correlated with comprises the preparation method and the equipment of CN03112408.9 continuous zirconia fiber, and CN200410024264.7 is organic to be gathered zirconium precursor body spinning solution and get rid of a legal system and be equipped with preparation method of preparation method, CN200910255807.9 one zirconia mesoporous fiber of sintering oven that Zirconium oxide fibre cotton, CN200410085390.3 be used to prepare continuous zirconia fiber, CN200910013781.7 complete stable cubic phase zircite crystal fibre and preparation method thereof, a CN200910013782.1 zirconia ceramic beaverboard etc.Wherein CN03112408.9, CN200410024262.7 and CN200910013781.7 adopt multiple solvent multistep preparation to gather acetyl acetone zirconium precursor body; Though realized suitability for industrialized production, technology is numerous and diverse relatively, causes product cost higher; Therefore, await further improvement.
Summary of the invention
To the deficiency of prior art, the present invention proposes to adopt a step solvent method to prepare Zirconium oxide fibre production to gather the zirconium precursor body or it gets rid of the method for a liquid with organic.The present invention gathers acetyl acetone zirconium legal system in existing patent employing to produce a kind of improved gordian technique that proposes on the basis of Zirconium oxide fibre fully.
Technical scheme of the present invention is following:
One step solvent method prepares organic method of gathering the zirconium precursor body, and step is following:
(1) eight hydration zirconium oxychlorides in molar ratio: part: precipitate and separate agent=1: (0.9-1.3): ratio (0.8-2.3); Take by weighing eight hydration zirconium oxychlorides, part and precipitate and separate agent respectively; Under 0 ~ 50 ℃ of temperature, agitation condition, join in the solvent, fully reaction obtains corresponding organic zirconium and hydrochloride of gathering; Suction filtration is removed the hydrochloride bullion, obtains organic zirconium solution that gathers;
(2) the organic zirconium solution that gathers of gained is carried out concentrating under reduced pressure recovery solvent at 20 ~ 50 ℃, obtain organic zirconium precursor body that gathers;
Said part is selected from methyl ethyl diketone, methyl aceto acetate or alcohol ether;
Said precipitate and separate agent is selected from C1-C5 straight or branched diamine, trolamine, ornithine or ammonia; Wherein said C1-C5 straight or branched diamine is a quadrol, 1,2-tn, 1,3-tn, tetramethylenediamine, pentamethylene diamine or their isomers;
Said solvent be C1-C4 alcohol a kind of or combination, C1-C4 is pure and mild and it can form combination or the mixed solvent of C1-C4 alcoholic solvent and high-carbon organic solvent and polymer formation of other solvents of azeotropic point;
Preferred in the step (1), when the precipitate and separate agent is C1-C5 straight or branched diamine, proportioning raw materials eight hydration zirconium oxychlorides: part: precipitate and separate agent=1: (0.9-1.3): (0.8-1.3).
Preferred in the step (1), when the precipitate and separate agent is trolamine, ornithine or ammonia, proportioning raw materials eight hydration zirconium oxychlorides: part: precipitate and separate agent=1: (0.9-1.3): (1.7-2.3).
Preferred in the step (1), the precipitate and separate agent is a quadrol, 1,2-tn or 1,3-tn.Further preferred precipitate and separate agent is a quadrol.
Preferred ligands is a methyl ethyl diketone in the step (1).
Part alcohol ether in the step (1) is methyl glycol, glycol monoethyl ether, propyl cellosolve, ethylene glycol monobutyl ether, terepthaloyl moietie one amyl ether, terepthaloyl moietie one hexyl ether, Rokafenol F 1, glycol monobenzyl ether, Ucar 35 monomethyl ether, propylene glycol monoethyl ether, Ucar 35 one propyl ether, Ucar 35 monobutyl ether, Ucar 35 one amyl ether, Ucar 35 one hexyl ether, Ucar 35 monophenyl ether or Ucar 35 monobenzyl ether.
Preferred in the step (1), described C1-C4 alcohol is straight or branched alcohol.Further preferred, described C1-C4 alcoholic solvent is one of methyl alcohol, ethanol, Virahol or its combination.
Preferred in the step (1), the adding total amount of said solvent is by weight the ratio of eight hydration zirconium oxychloride: solvent=100:400 ~ 900.
The described organic zirconium that gathers of step of the present invention (2) is for gathering the acetyl acetone zirconium, gathering that methyl aceto acetate closes zirconium or polyalcohol ether closes zirconium.Be used for Zirconium oxide fibre production.
On the other hand, organic the gathering in the zirconium precursor body that obtains in the step (2), can also add organic zirconium precursor body that gathers that phase stabilizer directly obtains containing phase stabilizer again, be used for Zirconium oxide fibre production; Also can in step (1), directly add organic zirconium precursor body that gathers that phase stabilizer obtains containing phase stabilizer.
Described phase stabilizer is muriate or the nitrate salt that described phase stabilizer is selected from yttrium, magnesium, calcium or cerium, and the dosage of phase stabilizer is counted 6-18mol% with the amount of substance ratio of total metal in yttrium, magnesium, calcium or cerium and the system.Further preferred, described phase stabilizer is selected from six hydration Yttrium trichlorides, magnesium chloride, calcium chloride or Cerium II Chloride.
The hydrochloride bullion that step of the present invention (1) suction filtration is removed adopts the pure water recrystallization to obtain the crystallization of high purity salt hydrochlorate.
One step solvent method prepares Zirconium oxide fibre production and gets rid of a liquid with organic zirconium precursor body that gathers, and the present invention provides following preferred version:
A. a step solvent method prepares Zirconium oxide fibre production and gathers the method that the zirconium precursor body gets rid of a liquid with organic, comprises the organic zirconium precursor body that gathers that utilizes method for preparing of the present invention, and the continuation step is following:
Prepared organic gathering adds phase stabilizer in proportion in the zirconium precursor body, with the stirring solvent dissolving, carry out concentrating under reduced pressure at 20 ~ 50 ℃ and reclaim solvent, obtains spinning property and gets rid of a liquid.Described phase stabilizer is selected from the muriate or the nitrate salt of yttrium, magnesium, calcium or cerium, and the dosage of phase stabilizer is counted 6-18mol% with the amount of substance ratio of total metal in yttrium, magnesium, calcium or cerium and the system; Further preferred, described phase stabilizer is selected from six hydration Yttrium trichlorides, magnesium chloride, calcium chloride or Cerium II Chloride, can make aftertreatment technology environmental protection more.
Further preferred, in the A method, described solvent is selected from C1-C4 straight or branched alcohol.Further preferred, said solvent is one of methyl alcohol, ethanol, Virahol or its combination.
B. a step solvent method prepares Zirconium oxide fibre production and gathers the method that the zirconium precursor body gets rid of a liquid with organic, and step is following:
Eight hydration zirconium oxychlorides in molar ratio: part: precipitate and separate agent: phase stabilizer=1: (0.9-1.3): (0.8-2.3): ratio (0.06-0.2); Take by weighing eight hydration zirconium oxychlorides, part, precipitate and separate agent and phase stabilizer; Under 0 ~ 50 ℃ of temperature; Join in the solvent at agitation condition, fully reaction obtains corresponding organic zirconium that gathers and gets rid of a liquid and crystal of hydrochloride.Suction filtration is removed the hydrochloride bullion, obtains organic zirconium that gathers and gets rid of a liquid.The hydrochloride bullion that suction filtration is removed adopts the pure water recrystallization to obtain the crystallization of high purity salt hydrochlorate.
In the B method, described part and precipitate and separate agent, preferably reach proportional range and above-mentioned organic gather in the zirconium precursor preparation step (1) identical: said part is selected from methyl ethyl diketone, methyl aceto acetate or alcohol ether; Said precipitate and separate agent is selected from C1-C5 straight or branched diamine, trolamine, ornithine or ammonia; Wherein said C1-C5 straight or branched diamine is a quadrol, 1,2-tn, 1,3-tn, tetramethylenediamine, pentamethylene diamine or their isomers.Selected solvent with above-mentioned organic gather in the zirconium precursor preparation identical: be C1-C4 alcohol a kind of or combination, C1-C4 is pure and mild and it can form combination or the mixed solvent of C1-C4 alcoholic solvent and high-carbon organic solvent and polymer formation of other solvents of azeotropic point, but add-on is according to weight ratio eight hydration zirconium oxychloride: solvent=100:100 ~ 900; Described phase stabilizer is selected from the muriate or the nitrate salt of yttrium, magnesium, calcium or cerium, and the dosage of phase stabilizer is counted 6-18mol% with the amount of substance ratio of total metal in yttrium, magnesium, calcium or cerium and the system.
Further preferred, in the B method, described phase stabilizer is selected from six hydration Yttrium trichlorides, magnesium chloride, calcium chloride or Cerium II Chloride; In a step solvent method; Cl ions in eight hydration zirconium oxychlorides and the phase stabilizer can be removed with the mode of hydrochloride by the precipitate and separate agent fully, and the nitrogen peroxide of also having avoided being produced in the fiber last handling process by the nitrate salt stablizer that uses in the previous patent is to the pollution of corrosion on Equipment and environment.
C, will contain organic zirconium precursor body stirring and dissolving in solvent of gathering of phase stabilizer, and carry out concentrating under reduced pressure at 20 ~ 50 ℃ and reclaim solvent, and obtain spinning property and get rid of a liquid.Said solvent is a C1-C4 alcohol, is preferably one of methyl alcohol, ethanol, Virahol or its combination, and solvent adding amount is according to weight ratio eight hydration zirconium oxychloride: solvent=100:100 ~ 400.
The present invention preparation organic gathers zirconium precursor body or its and gets rid of a liquid and be used for further producing the Zirconium oxide fibre material, and the preparation of subsequent oxidation zirconium filamentary material gets final product by prior art.For example centrifugal among CN03112408.9, CN200410024262.7 and the CN200910013781.7 gets rid of silk, fiber thermal treatment etc.
The present invention provides following and gathers the method that acetyl acetone zirconium, spinning solution prepare the Zirconium oxide fibre material by presoma:
The presoma that obtains gathered in the acetyl acetone zirconium solution add phase stabilizer; In temperature is 10 ~ 35 ℃, and centrifuge speed is 10000 ~ 30000r/min, gets rid of under the condition that an aperture is 0.1～0.5mm; Spinning solution is thrown away at a high speed from getting rid of a hole, obtain to gather acetyl acetone zirconium fiber.Place program control steam high-voltage sterilizing device to carry out the acetyl acetone zirconium fiber that gathers of above-mentioned acquisition in 2 ~ 6 normal atmosphere and 130 ~ 180 ℃ of preparatory dissection process; Fiber after the preparatory dissection process is placed in the program control thermal treatment sintering oven, in the presence of steam, be warming up to 500 ℃, be warming up to 1100 ~ 1600 ℃ with the temperature rise rate of 3 ℃/min with the temperature rise rate of 0.5 ℃/min, and insulation 1h; Gained fiber ZrO
2+ Y
2O
3Content is up to more than 99.95%, diameter 2 ~ 7 μ m, and 1 centimetre ~ 20 centimetres of length, intensity 0.6 ~ 1.1GPa can use under 2200 ℃ of temperature.
The present invention adopts a step solvent method to prepare organicly to gather the zirconium precursor body or it gets rid of a liquid; Be improvement, be applicable to that preparation gathers the acetyl acetone zirconium, gathers methyl aceto acetate and close zirconium and polyalcohol ether and close presoma such as zirconium series or get rid of a liquid and be used to produce Zirconium oxide fibre to the multiple solvent method of multistep of existing patent.The present invention reduces the simplification of Zirconium oxide fibre production technique, efficient raising, cost.
Technical characterstic of the present invention and excellent results are following:
The present invention uses organic or inorganic weak base; It is quadrol, 1; 2-tn, 1, replacements such as 3-tn, trolamine, ornithine or ammonia have the triethylamine (triethylamine hydrochloride is dissolved in methyl alcohol, ethanol and Virahol etc.) in the patent, utilize their hydrochloride (ethylenediamine-hydrochloride, 1; 2-tn hydrochloride, 1; 3-tn hydrochloride, triethanolamine hydrochloride, ornithine hydrochloride and ammonium chloride etc.) be insoluble in pure characteristics, can crystal of hydrochloride directly be separated with organic zirconium solution that gathers through the mode of suction filtration, direct concentrating obtains the presoma powder or gets rid of a liquid.Promptly adopt eight hydration zirconium oxychlorides as the zirconium source; Methyl ethyl diketone, methyl aceto acetate or alcohol ether are as part; Low-carbon alcohol such as methyl alcohol, ethanol, Virahol are as solvent; Choose quadrol, 1,2-tn, 1,3-tn, trolamine, ornithine or ammonia are as the precipitate and separate agent; Under suitable temperature, stirring, suction filtration and concentrating under reduced pressure condition, make organic zirconium (gather the acetyl acetone zirconium, gather methyl aceto acetate closes zirconium and polyalcohol ether closes zirconium etc.) that gathers, perhaps add yttrium salt, magnesium salts, calcium salt and cerium salt etc. and make spinning property as phase stabilizer and get rid of a liquid.
Inventing preferred precipitate and separate agent makes the by-product salt hydrochlorate be insoluble to alcohol.Thereby, can be used for eliminating all cl ionss of eight hydration zirconium oxychlorides and phase stabilizer; And omitted the multiple solvents that separate such as acetone, THF and normal hexane, reduced raw materials cost significantly; Reduced pollution to corrosion on Equipment and environment.
The present invention's " step solvent method " except keeping existing patent to prepare presoma or getting rid of the advantage of a liquid, also has notable features such as the technical process of making simplification, cost reduction, productive rate raising, quality optimization and environmental protection.
Description of drawings
Fig. 1 is that the presoma of embodiment 1 preparation gathers acetyl acetone zirconium photo;
Fig. 2 is the crystal of zirconium oxide fiber photo that embodiment 20 usefulness presomas gather the preparation of acetyl acetone zirconium;
Fig. 3 is that the organic zirconium that gathers of embodiment 100 usefulness gets rid of a photo of the crystal of zirconium oxide fiber of liquid preparation.
Embodiment
Through more typical embodiment the present invention is further specified below, but be not limited only to this.
Embodiment 1:
Take by weighing 100g eight hydration zirconium oxychlorides, 31.1g methyl ethyl diketone and 18.6g quadrol respectively; Join in the 880g methyl alcohol fully reaction 3 hours at 0 ~ 50 ℃, agitation condition; Obtain gathering acetyl acetone zirconium and ethylenediamine-hydrochloride, suction filtration is removed the ethylenediamine-hydrochloride bullion, obtains gathering the methanol solution of acetyl acetone zirconium; Gained solution is carried out concentrating under reduced pressure at 20 ~ 50 ℃ reclaim methyl alcohol, obtain flaxen presoma and gather acetyl acetone zirconium 74.3g (like Fig. 1); The ethylenediamine-hydrochloride bullion that suction filtration is removed adopts the pure water recrystallization to obtain high purity ethylenediamine-hydrochloride crystallization 39.8g, purity 99.0%.
Embodiment 2:
Of embodiment 1, different is the alcohol solvent that methanol solvate changes 880g into.Obtain flaxen presoma behind the concentrating under reduced pressure and gather acetyl acetone zirconium 74.6g; The ethylenediamine-hydrochloride bullion that suction filtration is removed adopts the pure water recrystallization to obtain high purity ethylenediamine-hydrochloride crystallization 40.1g, purity 99.0%.
Embodiment 3:
Of embodiment 1, different is that methyl alcohol changes Virahol into, makes flaxen presoma and gathers the acetyl acetone zirconium.
Embodiment 4:
Of embodiment 1, different is that methyl alcohol changes n-propyl alcohol into, makes flaxen presoma and gathers the acetyl acetone zirconium.
Embodiment 5:
Of embodiment 1, different is that methyl alcohol changes the trimethyl carbinol into, makes flaxen presoma and gathers the acetyl acetone zirconium.
Embodiment 6:
Of embodiment 1, different is that methyl alcohol changes sec-butyl alcohol into, makes flaxen presoma and gathers the acetyl acetone zirconium.
Embodiment 7:
Of embodiment 1, different is that methyl alcohol changes isopropylcarbinol into, makes flaxen presoma and gathers the acetyl acetone zirconium.
Embodiment 8:
Of embodiment 1, different is that methyl alcohol changes propyl carbinol into, makes flaxen presoma and gathers the acetyl acetone zirconium.
Embodiment 9:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes methyl alcohol and ethanol 9:1 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 10:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes methyl alcohol and ethanol 1:4 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 11:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes methyl alcohol and Virahol 8:1 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 12:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes ethanol and Virahol 1:1 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 13:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes methyl alcohol, ethanol and Virahol 2:1:1 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 14:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes methyl alcohol and terepthaloyl moietie 99:1 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 15:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes ethanol and acetone 99:1 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 16:
Of embodiment 1, different is the mixed solvent that methyl alcohol changes ethanol and normal hexane 15:2 volume ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 17:
Of embodiment, different methyl alcohol change the mixed solvent of methyl alcohol and Z 150PH (PVA) 100:1 weight ratio into.Make flaxen presoma and gather the acetyl acetone zirconium.
Embodiment 18:
Take by weighing 100g eight hydration zirconium oxychlorides, 31.1g methyl ethyl diketone, 11.3g six hydration Yttrium trichlorides and 22.0g quadrol respectively; Join in the 880g ethanol fully reaction 3 hours at 0 ~ 50 ℃, agitation condition; What obtain containing yttrium gathers acetyl acetone zirconium and ethylenediamine-hydrochloride; Suction filtration is removed the ethylenediamine-hydrochloride bullion; Obtain containing the ethanolic soln that gathers the acetyl acetone zirconium of yttrium, gained solution is carried out concentrating under reduced pressure at 20 ~ 50 ℃ reclaim ethanol, what obtain that flaxen presoma contains yttrium gathers acetyl acetone zirconium 87.2g (like Fig. 1); The ethylenediamine-hydrochloride bullion that suction filtration is removed adopts the pure water recrystallization to obtain high purity ethylenediamine-hydrochloride crystallization 47.4g, purity 99.0%.
Embodiment 19:
Of embodiment 1, the flaxen presoma that different is will obtain gathers and adds 11.3g six hydration Yttrium trichlorides among the acetyl acetone zirconium 74.3g, together fully is dissolved in obtaining presoma in the 80g methyl alcohol and getting rid of a liquid.
It is 25 ℃ in temperature that presoma is got rid of a liquid, and centrifuge speed is 15000r/min, and getting rid of a hole LV is 30m/s, gets rid of under the condition that an aperture is 0.2mm, and spinning solution is thrown away at a high speed from getting rid of a hole, obtains to gather acetyl acetone zirconium fiber.Place program control steam high-voltage sterilizing pot to carry out the acetyl acetone zirconium fiber that gathers of above-mentioned acquisition in 2.2 normal atmosphere and 134 ℃ of preparatory dissection process; The fiber of preparatory dissection process is placed in the quartzy sintering oven of program control thermal treatment; In the presence of steam, be warming up to 500 ℃ with the temperature rise rate of 0.5 ℃/min, be warming up to 1600 ℃ with the temperature rise rate of 3 ℃/min; And insulation 1h, can obtain high purity, the full grown crystal of zirconium oxide fiber of crystal grain.
Embodiment 20:
Of embodiment 2, the flaxen presoma that different is will obtain gathers and adds 11.3g six hydration Yttrium trichlorides among the acetyl acetone zirconium 74.6g, together fully is dissolved in obtaining presoma in the 80g ethanol and getting rid of a liquid.
It is 28 ℃ in temperature that presoma gets rid of a liquid, and centrifuge speed is 16000r/min, and getting rid of a hole LV is 35m/s, gets rid of under the condition that an aperture is 0.25mm, and spinning solution is thrown away at a high speed from getting rid of a hole, obtains to gather acetyl acetone zirconium fiber.Place program control steam high-voltage sterilizing pot to carry out the acetyl acetone zirconium fiber that gathers of above-mentioned acquisition in 2.2 normal atmosphere and 134 ℃ of preparatory dissection process; The fiber of preparatory dissection process is placed in the quartzy sintering oven of program control thermal treatment; In the presence of steam, be warming up to 500 ℃ with the temperature rise rate of 0.5 ℃/min, be warming up to 1600 ℃ with the temperature rise rate of 3 ℃/min; And insulation 1h, can obtain high purity, the full grown crystal of zirconium oxide fiber of crystal grain.Crystal of zirconium oxide fiber photo such as Fig. 2.
Embodiment 21:
Of embodiment 18, the presoma that contains yttrium that different is will obtain gathers acetyl acetone zirconium 87.2g and fully is dissolved in and obtains presoma in the 80g ethanol and get rid of a liquid.
It is 28 ℃ in temperature that presoma gets rid of a liquid, and centrifuge speed is 18000r/min, and getting rid of a hole LV is 26m/s, gets rid of under the condition that an aperture is 0.3mm, and spinning solution is thrown away at a high speed from getting rid of a hole, obtains to gather acetyl acetone zirconium fiber.Place program control steam high-voltage sterilizing pot to carry out the acetyl acetone zirconium fiber that gathers of above-mentioned acquisition in 2.2 normal atmosphere and 134 ℃ of preparatory dissection process; The fiber of preparatory dissection process is placed in the quartzy sintering oven of program control thermal treatment; In the presence of steam, be warming up to 500 ℃ with the temperature rise rate of 0.5 ℃/min, be warming up to 1600 ℃ with the temperature rise rate of 3 ℃/min; And insulation 1h, can obtain high purity, the full grown crystal of zirconium oxide fiber of crystal grain.
Embodiment 22:
Take by weighing 100g eight hydration zirconium oxychlorides, 31.1g methyl ethyl diketone and 23.0g1 respectively, the 2-tn joins in the 880g ethanol fully reaction 4 hours at 0 ~ 50 ℃, agitation condition; Obtain gathering acetyl acetone zirconium and 1,2-tn hydrochloride, suction filtration removes 1; 2-tn hydrochloride bullion; Obtain gathering the ethanolic soln of acetyl acetone zirconium, gained solution is carried out concentrating under reduced pressure at 20 ~ 50 ℃ reclaim ethanol, obtain flaxen presoma and gather the acetyl acetone zirconium; Suction filtration remove 1,2-tn hydrochloride bullion adopts the pure water recrystallization to obtain high purity 1,2-tn crystal of hydrochloride.
Embodiment 23:
Of embodiment 22, different is to take by weighing 23.0g1, and the 2-tn changes into and takes by weighing 23.0g1, the 3-tn.Obtain flaxen presoma and gather the acetyl acetone zirconium; Suction filtration remove 1,3-tn hydrochloride bullion adopts the pure water recrystallization to obtain high purity 1,2-tn crystal of hydrochloride.
Embodiment 24:
Of embodiment 22, different is 1, and the 2-tn changes the 92.5g trolamine into, because trolamine is slightly soluble in ethanol, and remaining a small amount of triethanolamine hydrochloride in the filtrating.
Embodiment 25:
Of embodiment 22, different is 1, and the 2-tn changes the 82.9g ornithine into.What obtain at last is that flaxen presoma gathers acetyl acetone zirconium 74.4g, ornithine hydrochloride crystallization 104.3g.
Embodiment 26:
Of embodiment 22, different is with 1, and the 2-tn changes into and slowly feeds the 10.5g ammonia, and the flaxen presoma that obtains gathers acetyl acetone zirconium 73.8g, ammonium chloride crystals 30.1g.Remaining ammonium chloride more (because ammonium chloride is slightly soluble in ethanol) in the filtrating.
Embodiment 27:
Take by weighing 100g eight hydration zirconium oxychlorides, 31.1g methyl ethyl diketone and 109.2g l-arginine respectively; Join in the 880g methyl alcohol fully reaction 10 hours at 0 ~ 50 ℃, agitation condition; Obtain gathering acetyl acetone zirconium and arginine monohydrochloride; Suction filtration is removed the arginine monohydrochloride bullion, obtains the flaxen methanol solution that gathers the acetyl acetone zirconium, gained solution is carried out concentrating under reduced pressure at 20 ~ 50 ℃ reclaim methyl alcohol; Obtain flaxen presoma and gather the acetyl acetone zirconium, arginine monohydrochloride recrystallization in water is purified.There is the part l-arginine remaining in the arginine monohydrochloride.
Embodiment 28:
Of embodiment 27, different is to take by weighing the 109.2g l-arginine to change 91.6g Methionin into.Obtain flaxen acetyl acetone zirconium precursor body and the lysine hydrochloride of gathering.
Embodiment 29:
Of embodiment 27, different is to take by weighing the 109.2g l-arginine to change the 97.2g Histidine into.Obtain flaxen acetyl acetone zirconium precursor body and the L-Histidine hydrochloride of gathering.
Embodiment 30:
Take by weighing 100g eight hydration zirconium oxychlorides, 40.4g methyl aceto acetate and 18.6g quadrol respectively; Join in the 880g Virahol fully reaction 4.5 hours at 0 ~ 50 ℃, agitation condition; Obtain gathering methyl aceto acetate and close zirconium and ethylenediamine-hydrochloride; Suction filtration is removed the ethylenediamine-hydrochloride bullion; Obtain the flaxen aqueous isopropanol that methyl aceto acetate closes zirconium that gathers, gained solution is carried out concentrating under reduced pressure at 20 ~ 50 ℃ reclaim Virahol, obtain flaxen presoma and gather methyl aceto acetate and close zirconium 83.4g; The ethylenediamine-hydrochloride bullion that suction filtration is removed adopts the pure water recrystallization to obtain the crystallization of high purity ethylenediamine-hydrochloride.
Embodiment 31:
Take by weighing 100g eight hydration zirconium oxychlorides, 23.6g methyl glycol (part) and 18.6g quadrol respectively; Join in the 880g ethanol fully reaction 4 hours at 0 ~ 50 ℃, agitation condition; Obtain the polyoxyethylene glycol monomethyl ether and close zirconium and ethylenediamine-hydrochloride; Suction filtration is removed the ethylenediamine-hydrochloride bullion; Obtain the aqueous isopropanol that flaxen polyoxyethylene glycol monomethyl ether closes zirconium, gained solution is carried out concentrating under reduced pressure at 20 ~ 50 ℃ reclaim ethanol, obtain flaxen presoma polyoxyethylene glycol monomethyl ether and close zirconium 66.5g; The ethylenediamine-hydrochloride bullion that suction filtration is removed adopts the pure water recrystallization to obtain the crystallization of high purity ethylenediamine-hydrochloride.
Embodiment 32:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing the 28.0g glycol monoethyl ether.
Embodiment 33:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing the 32.3g propyl cellosolve.
Embodiment 34:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing the 36.7g ethylene glycol monobutyl ether.
Embodiment 35:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 42.0g terepthaloyl moietie one amyl ether.
Embodiment 36:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 45.1g terepthaloyl moietie one hexyl ether.
Embodiment 37:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing the 42.9g Rokafenol F 1.
Embodiment 38:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing the 47.3g glycol monobenzyl ether.
Embodiment 39:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 28.0g Ucar 35 monomethyl ether.
Embodiment 40:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing the 32.3g propylene glycol monoethyl ether.
Embodiment 41:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 36.7g Ucar 35 one propyl ether.
Embodiment 42:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 42.0g Ucar 35 monobutyl ether.
Embodiment 43:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 45.1g Ucar 35 one amyl ether.
Embodiment 44:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 49.7g Ucar 35 one hexyl ether.
Embodiment 45:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 47.3g Ucar 35 monophenyl ether.
Embodiment 46:
Of embodiment 31, different is, and methyl glycol changes into takes by weighing 51.6g Ucar 35 monobenzyl ether.
Above embodiment 30-46 obtains different presomas, tabulates as follows:
| Embodiment | Presoma (weight g) |
| 30 | Gather methyl aceto acetate and close zirconium (83.4g) |
| 31 | The polyoxyethylene glycol monomethyl ether closes zirconium (66.5g) |
| 32 | Polyoxyethylene glycol one ether closes zirconium (70.8g) |
| 33 | Polyoxyethylene glycol one propyl ether closes zirconium (75.0g) |
| 34 | The polyoxyethylene glycol monobutyl ether closes zirconium (79.4g) |
| 35 | Polyoxyethylene glycol one amyl ether closes zirconium (83.3g) |
| 36 | Polyoxyethylene glycol one hexyl ether closes zirconium (87.6g) |
| 37 | The polyoxyethylene glycol monophenyl ether closes zirconium (85.2g) |
| 38 | The polyoxyethylene glycol monobenzyl ether closes zirconium (89.8g) |
| 39 | The W 166 monomethyl ether closes zirconium (70.5g) |
| 40 | W 166 one ether closes zirconium (74.7g) |
| 41 | W 166 one propyl ether closes zirconium (78.9g) |
| 42 | The W 166 monobutyl ether closes zirconium (82.7g) |
| 43 | W 166 one amyl ether closes zirconium (87.0) |
| 44 | W 166 one hexyl ether closes zirconium (92.1) |
| 45 | The W 166 monophenyl ether closes zirconium (89.5) |
| 46 | The W 166 monobenzyl ether closes zirconium (94.3) |
Embodiment 47:
Of embodiment 1, different is that 880g methyl alcohol changes 800g methyl alcohol into.
Embodiment 48:
Of embodiment 1, different is that 880g methyl alcohol changes 600g methyl alcohol into.
Embodiment 49:
Of embodiment 1, different is that 880g methyl alcohol changes 400g methyl alcohol into.
Embodiment 50:
At 0 ~ 50 ℃; Take by weighing 100g eight hydration zirconium oxychlorides, 31.1g methyl ethyl diketone, 11.3g six hydration Yttrium trichlorides and 22.0g quadrol respectively and add fully reaction in the 160g methyl alcohol; Obtain gathering acetyl acetone zirconium and ethylenediamine-hydrochloride, suction filtration is removed the ethylenediamine-hydrochloride bullion and is obtained gathering the acetyl acetone zirconium solution, gained solution is carried out concentrating under reduced pressure at 20 ~ 50 ℃ reclaim methyl alcohol; Obtain golden yellow spinning property and get rid of a liquid, the ethylenediamine-hydrochloride bullion adopts the pure water recrystallization to obtain its high-purity crystallization.
Embodiment 51:
Of embodiment 50, different is that methyl alcohol changes ethanol into.
Embodiment 52:
Of embodiment 50, different is that methyl alcohol changes Virahol into.
Embodiment 53:
Of embodiment 50, different is that methyl alcohol changes n-propyl alcohol into.
Embodiment 54:
Of embodiment 50, different is that methyl alcohol changes the trimethyl carbinol into.
Embodiment 55:
Of embodiment 50, different is that methyl alcohol changes sec-butyl alcohol into.
Embodiment 56:
Of embodiment 50, different is that methyl alcohol changes isopropylcarbinol into.
Embodiment 57:
Of embodiment 50, different is that methyl alcohol changes propyl carbinol into.
Embodiment 58:
Of embodiment 50, different is the mixed solvent that methanol solvate changes methyl alcohol and ethanol 4:1 volume ratio into.
Embodiment 59:
Of embodiment 50, different is the mixed solvent that methanol solvate changes methyl alcohol and ethanol 1:7 volume ratio into.
Embodiment 60:
Of embodiment 50, different is the mixed solvent that methanol solvate changes methyl alcohol and Virahol 6:1 volume ratio into.
Embodiment 61:
Of embodiment 50, different is the mixed solvent that methanol solvate changes ethanol and Virahol 3:1 volume ratio into.
Embodiment 62:
Of embodiment 50, different is the mixed solvent that methanol solvate changes methyl alcohol, ethanol and Virahol 5:3:1 volume ratio into.
Embodiment 63:
Of embodiment 50, different is the mixed solvent that methanol solvate changes ethanol, Virahol and trimethyl carbinol 2:1:1 volume ratio into.
Embodiment 64:
Of embodiment 50, different is the mixed solvent that methanol solvate changes methyl alcohol and USP Kosher 99:1 volume ratio into.
Embodiment 65:
Of embodiment 50, different is the mixed solvent that methanol solvate changes ethanol and methyl-sulphoxide 99:1 volume ratio into.
Embodiment 66:
Of embodiment 50, different is the mixed solvent that methanol solvate changes ethanol and hexanaphthene 7:1 volume ratio into.
Embodiment 67:
Of embodiment 50, different methanol solvates change the mixed solvent of methyl alcohol and Vinylpyrrolidone polymer (PVP) 100:1 weight ratio into.
Embodiment 68:
Of embodiment 50, different is, and quadrol changes into takes by weighing 1 of 27.2g, the 2-tn.
Embodiment 69:
Of embodiment 50, different is, and quadrol changes into takes by weighing 27.2g 1, the 3-tn.
Embodiment 70:
Of embodiment 50, different is that quadrol changes the 109.4g trolamine into.
Embodiment 71:
Of embodiment 50, different is that quadrol changes the 98.0g ornithine into.
Embodiment 72:
Of embodiment 50, different is, and quadrol changes into slowly feeds the 12.4g ammonia.
Embodiment 73:
Of embodiment 50, different is that methyl ethyl diketone changes the 40.4g methyl aceto acetate into, gets rid of a liquid spinning property basically with embodiment 50.
Embodiment 74:
Of embodiment 50, different is that methyl ethyl diketone changes the 23.6g methyl glycol into, and the spinning property spinning property of getting rid of a liquid is worse than 50 slightly.
Embodiment 75:
Of embodiment 50, different is that methyl ethyl diketone changes the 28.0g glycol monoethyl ether into, and the spinning property of getting rid of a liquid is with embodiment 74.
Embodiment 76:
Of embodiment 50, different is that methyl ethyl diketone changes the 32.3g propyl cellosolve into, and the spinning property of getting rid of a liquid is with embodiment 74.
Embodiment 77:
Of embodiment 50, different is that methyl ethyl diketone changes the 36.7g ethylene glycol monobutyl ether into, and the spinning property of getting rid of a liquid is with embodiment 74.
Embodiment 78:
Of embodiment 50, different is that methyl ethyl diketone changes 42.0g terepthaloyl moietie one amyl ether into, and the spinning property of getting rid of a liquid is with embodiment 74.
Embodiment 79:
Of embodiment 50, different is that methyl ethyl diketone changes 45.1g terepthaloyl moietie one hexyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 80:
Of embodiment 50, different is that methyl ethyl diketone changes the 42.9g Rokafenol F 1 into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 81:
Of embodiment 50, different is that methyl ethyl diketone changes the 47.3g glycol monobenzyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 82:
Of embodiment 50, different is that methyl ethyl diketone changes 28.0g Ucar 35 monomethyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 83:
Of embodiment 50, different is that methyl ethyl diketone changes the 32.3g propylene glycol monoethyl ether into, gets rid of the spinning property of a liquid, basically with embodiment 74.
Embodiment 84:
Of embodiment 50, different is that methyl ethyl diketone changes 36.7g Ucar 35 one propyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 85:
Of embodiment 50, different is that methyl ethyl diketone changes 42.0g Ucar 35 monobutyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 86:
Of embodiment 50, different is that methyl ethyl diketone changes 45.1g Ucar 35 one amyl ether into, and the spinning property of getting rid of a liquid is more basically with embodiment 74.
Embodiment 87:
Of embodiment 50, different is that methyl ethyl diketone changes 49.7g Ucar 35 one hexyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 88:
Of embodiment 50, different is that methyl ethyl diketone changes 47.3g Ucar 35 monophenyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 89:
Of embodiment 50, different is that methyl ethyl diketone changes 51.6g Ucar 35 monobenzyl ether into, and the spinning property of getting rid of a liquid is basically with embodiment 74.
Embodiment 90:
Of embodiment 50, different is that 11.3g six hydration Yttrium trichlorides change 12.6g six hydration Yttrium trichlorides into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 91:
Of embodiment 50, different is that 11.3g six hydration Yttrium trichlorides change 11.9g six hydration Yttrium trichlorides into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 92:
Of embodiment 50, different is that 11.3g six hydration Yttrium trichlorides change 10.1g six hydration Yttrium trichlorides into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 93:
Of embodiment 50, different is that 11.3g six hydration Yttrium trichlorides change 6.5g six hydration Yttrium trichlorides into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 94:
Of embodiment 50, different is that 11.3g six hydration Yttrium trichlorides change 18.0g six hydration Yttrium trichlorides into, and the spinning property of getting rid of a liquid is worse than embodiment 50 slightly.
Embodiment 95:
Of embodiment 50, different is that 160g methyl alcohol changes 850g methyl alcohol into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 96:
Of embodiment 50, different is that 160g methyl alcohol changes 600g methyl alcohol into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 97:
Of embodiment 50, different is that 160g methyl alcohol changes 320g methyl alcohol into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 98:
Of embodiment 50, different is that 160g methyl alcohol changes 200g methyl alcohol into, and the spinning property of getting rid of a liquid is with embodiment 50.
Embodiment 99:
Of embodiment 50, different is that 160g methyl alcohol changes 120g methyl alcohol into, and the spinning property of getting rid of a liquid is basically with embodiment 50.
Embodiment 100:
Of embodiment 50, different is, and gained gets rid of that a liquid continues in temperature is 27 ℃, and centrifuge speed is 17000r/min; Getting rid of a hole LV is 33m/s; Get rid of under the condition that an aperture is 0.2mm, spinning solution is thrown away at a high speed from getting rid of a hole, obtain to gather acetyl acetone zirconium fiber.Place program control steam high-voltage sterilizing pot to carry out the acetyl acetone zirconium fiber that gathers of above-mentioned acquisition in 2.2 normal atmosphere and 134 ℃ of preparatory dissection process; The fiber of preparatory dissection process is placed in the quartzy sintering oven of program control thermal treatment; In the presence of steam, be warming up to 500 ℃ with the temperature rise rate of 0.5 ℃/min, be warming up to 1600 ℃ with the temperature rise rate of 3 ℃/min; And insulation 1h, can obtain high purity, the full grown crystal of zirconium oxide fiber of crystal grain.Crystal of zirconium oxide fiber photo such as Fig. 3.
Claims (10)
1. a step solvent method prepares organic method of gathering the zirconium precursor body, and step is following:
(1) eight hydration zirconium oxychlorides in molar ratio: part: precipitate and separate agent=1: (0.9-1.3): ratio (0.8-2.3); Take by weighing eight hydration zirconium oxychlorides, part and precipitate and separate agent respectively; Under 0 ~ 50 ℃ of temperature, agitation condition, join in the solvent, fully reaction obtains corresponding organic zirconium and hydrochloride of gathering; Suction filtration is removed crystal of hydrochloride, obtains organic zirconium solution that gathers;
(2) the organic zirconium solution that gathers of gained is carried out concentrating under reduced pressure recovery solvent at 20 ~ 50 ℃, obtain organic zirconium precursor body that gathers;
Said part is selected from methyl ethyl diketone, methyl aceto acetate or alcohol ether;
Said precipitate and separate agent is selected from C1-C5 straight or branched diamine, trolamine, ornithine or ammonia; Wherein said C1-C5 straight or branched diamine is a quadrol, 1,2-tn, 1,3-tn, tetramethylenediamine, pentamethylene diamine or their isomers;
Said solvent be C1-C4 alcohol a kind of or combination, C1-C4 is pure and mild and it can form combination or the mixed solvent of C1-C4 alcoholic solvent and high-carbon organic solvent and polymer formation of other solvents of azeotropic point;
Perhaps in the product of step (2), add phase stabilizer, obtain containing organic zirconium precursor body that gathers of phase stabilizer;
Perhaps in the reactant of step (1), add phase stabilizer, finally obtain containing organic zirconium precursor body that gathers of phase stabilizer;
Described phase stabilizer is selected from the muriate or the nitrate salt of yttrium, magnesium, calcium or cerium.
2. the organic method of gathering the zirconium precursor body of preparation as claimed in claim 1; When it is characterized in that precipitate and separate agent in the step (1) is C1-C5 straight or branched diamine, proportioning raw materials eight hydration zirconium oxychlorides: part: precipitate and separate agent=1: (0.9-1.3): (0.8-1.3).
3. the organic method of gathering the zirconium precursor body of preparation as claimed in claim 1; When it is characterized in that precipitate and separate agent in the step (1) is trolamine, ornithine or ammonia, proportioning raw materials eight hydration zirconium oxychlorides: part: precipitate and separate agent=1: (0.9-1.3): (1.7-2.3).
4. the organic method of gathering the zirconium precursor body of preparation as claimed in claim 1 is characterized in that the precipitate and separate agent in the step (1) is a quadrol, 1,2-tn or 1,3-tn; Preferred precipitate and separate agent is a quadrol.
5. the organic method of gathering the zirconium precursor body of preparation as claimed in claim 1 is characterized in that the preferred methyl ethyl diketone of part described in the step (1).
6. the organic method of gathering the zirconium precursor body of preparation as claimed in claim 1 is characterized in that the C1-C4 alcohol described in the step (1) is straight or branched alcohol; Preferably, C1-C4 alcohol is one of methyl alcohol, ethanol, Virahol or its combination.
7. the organic method of gathering the zirconium precursor body of preparation as claimed in claim 1 is characterized in that the ratio of the adding total amount of solvent described in the step (1) by weight eight hydration zirconium oxychloride: solvent=100:400 ~ 900.
8. a step solvent method prepares Zirconium oxide fibre production and gathers the method that the zirconium precursor body gets rid of a liquid with organic, comprise claim 1 ~ 7 each, it is characterized in that also comprising the steps:
Organic the gathering that makes in step (2) adds phase stabilizer in proportion in the zirconium precursor body, add the stirring solvent dissolving, carries out concentrating under reduced pressure at 20 ~ 50 ℃ and reclaims solvent, obtains spinning property and gets rid of a liquid; Described phase stabilizer is selected from the muriate or the nitrate salt of yttrium, magnesium, calcium or cerium, and the dosage of phase stabilizer is counted 6-18mol% with the amount of substance ratio of total metal in yttrium, magnesium, calcium or cerium and the system;
Perhaps, in step (1), directly add organic zirconium precursor body that gathers that phase stabilizer obtains containing phase stabilizer, organic zirconium precursor body that gathers that will contain phase stabilizer adds the stirring solvent dissolving, carries out concentrating under reduced pressure at 20 ~ 50 ℃ and reclaims solvent, obtains spinning property and gets rid of a liquid.
9. organic preparation method that the zirconium precursor body gets rid of a liquid that gathers as claimed in claim 8 is characterized in that described phase stabilizer is selected from six hydration Yttrium trichlorides, magnesium chloride, calcium chloride or Cerium II Chloride;
Said solvent is a C1-C4 alcohol, is preferably one of methyl alcohol, ethanol, Virahol or its combination, and solvent adding amount is according to weight ratio eight hydration zirconium oxychloride: solvent=100:100 ~ 900.
10. a step solvent method prepares Zirconium oxide fibre production and gets rid of a liquid with organic zirconium precursor body that gathers, and step is following:
Eight hydration zirconium oxychlorides in molar ratio: part: precipitate and separate agent: phase stabilizer=1: (0.9-1.3): (0.8-2.3): ratio (0.06-0.2); Take by weighing eight hydration zirconium oxychlorides, part, precipitate and separate agent and phase stabilizer; Under 0 ~ 50 ℃ of temperature; Join in the solvent at agitation condition, fully reaction obtains corresponding organic zirconium that gathers and gets rid of a liquid and crystal of hydrochloride.Suction filtration is removed the hydrochloride bullion, obtains organic zirconium that gathers and gets rid of a liquid; The hydrochloride bullion that suction filtration is removed adopts the pure water recrystallization to obtain the crystallization of high purity salt hydrochlorate;
Described part and precipitate and separate agent and claim 1 ~ 8 said organic gather in the zirconium precursor preparation identical; Selected solvent is also identical, and solvent adding amount is according to weight ratio eight hydration zirconium oxychloride: solvent=100:100 ~ 900;
Described phase stabilizer is selected from the muriate or the nitrate salt of yttrium, magnesium, calcium or cerium; Preferred described phase stabilizer is selected from six hydration Yttrium trichlorides, magnesium chloride, calcium chloride or Cerium II Chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210264131.1A CN102766154B (en) | 2012-07-28 | 2012-07-28 | Method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210264131.1A CN102766154B (en) | 2012-07-28 | 2012-07-28 | Method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102766154A true CN102766154A (en) | 2012-11-07 |
| CN102766154B CN102766154B (en) | 2015-04-22 |
Family
ID=47093761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210264131.1A Expired - Fee Related CN102766154B (en) | 2012-07-28 | 2012-07-28 | Method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102766154B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103993388A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | High-temperature pressure resolution technology for preparing high-performance zirconia crystal fiber |
| CN103993387A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing ultrahigh-temperature-resistant kilometric continuous zirconia crystal fiber |
| CN104961763A (en) * | 2015-07-17 | 2015-10-07 | 山东大学 | Method for preparing titanium dioxide fiber with excellent photocatalytic performance, precursor and spinning solution by virtue of one-step solvent method |
| CN109868526A (en) * | 2018-12-28 | 2019-06-11 | 山东大学 | A kind of method that zirconium-yttrium polymer precursor prepares zirconic acid yttrium nanofiber |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01132831A (en) * | 1987-11-12 | 1989-05-25 | Kanichi Kamiya | Method for producing zirconia fiber |
| CA2026523A1 (en) * | 1989-09-30 | 1991-03-31 | Helmut Scharf | Zirconium dioxide powder, processes for its preparation, its use and sintered articles produced therefrom |
| JPH042658A (en) * | 1990-04-17 | 1992-01-07 | Nippon Soda Co Ltd | High-strength colored zirconia sintered material and production thereof |
| CN1584155A (en) * | 2004-06-11 | 2005-02-23 | 山东大学 | Zirconium oxide fabrics prepared from organic polyzirconium fore spinning solution by silk process |
| CN1919813A (en) * | 2005-08-27 | 2007-02-28 | H.C.施塔克股份有限公司 | Process for the preparation of high-purity zirconium, hafnium, tantalum and niobium alkoxides |
| CN1948163A (en) * | 2006-11-09 | 2007-04-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of zirconium oxide colloidal sol |
| CN101498063A (en) * | 2009-01-14 | 2009-08-05 | 济南大学 | Preparation of complete stable cubic phase zircite crystal fibre |
| CN102249304A (en) * | 2010-05-21 | 2011-11-23 | 张永昶 | Method for preparing spherical nanometer zirconium dioxide |
-
2012
- 2012-07-28 CN CN201210264131.1A patent/CN102766154B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01132831A (en) * | 1987-11-12 | 1989-05-25 | Kanichi Kamiya | Method for producing zirconia fiber |
| CA2026523A1 (en) * | 1989-09-30 | 1991-03-31 | Helmut Scharf | Zirconium dioxide powder, processes for its preparation, its use and sintered articles produced therefrom |
| JPH042658A (en) * | 1990-04-17 | 1992-01-07 | Nippon Soda Co Ltd | High-strength colored zirconia sintered material and production thereof |
| CN1584155A (en) * | 2004-06-11 | 2005-02-23 | 山东大学 | Zirconium oxide fabrics prepared from organic polyzirconium fore spinning solution by silk process |
| CN1919813A (en) * | 2005-08-27 | 2007-02-28 | H.C.施塔克股份有限公司 | Process for the preparation of high-purity zirconium, hafnium, tantalum and niobium alkoxides |
| CN1948163A (en) * | 2006-11-09 | 2007-04-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of zirconium oxide colloidal sol |
| CN101498063A (en) * | 2009-01-14 | 2009-08-05 | 济南大学 | Preparation of complete stable cubic phase zircite crystal fibre |
| CN102249304A (en) * | 2010-05-21 | 2011-11-23 | 张永昶 | Method for preparing spherical nanometer zirconium dioxide |
Non-Patent Citations (4)
| Title |
|---|
| HE-YI LIU,等: "Fabrication of High-Strength Continuous Zirconia Fibers and Their Formation Mechanism Study", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
| XUEYU TAO，等: "Synthesis of nanosized zirconium carbide from preceramic polymers by the facile one-pot reaction", 《POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
| 张旺玺，等: "氧化锆纤维的制备、性能和应用", 《合成技术及应用》 * |
| 潘梅，等: "ZrO2连续纤维研究进展", 《硅酸盐通报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103993388A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | High-temperature pressure resolution technology for preparing high-performance zirconia crystal fiber |
| CN103993387A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing ultrahigh-temperature-resistant kilometric continuous zirconia crystal fiber |
| CN103993387B (en) * | 2014-05-30 | 2016-08-17 | 山东大学 | A kind of preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level |
| CN104961763A (en) * | 2015-07-17 | 2015-10-07 | 山东大学 | Method for preparing titanium dioxide fiber with excellent photocatalytic performance, precursor and spinning solution by virtue of one-step solvent method |
| CN109868526A (en) * | 2018-12-28 | 2019-06-11 | 山东大学 | A kind of method that zirconium-yttrium polymer precursor prepares zirconic acid yttrium nanofiber |
| CN109868526B (en) * | 2018-12-28 | 2021-05-28 | 山东大学 | Method for preparing yttrium zirconate nanofiber by using zirconium-yttrium polymer precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102766154B (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Copper-catalyzed radical cascades of para-quinone methides with AIBN and H 2 O via α-cyanoalkylation by C–C bond cleavage: new access to benzofuran-2 (3 H)-ones | |
| CN102766154B (en) | Method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method | |
| CN102557628B (en) | Flexible yttrium stable zirconium oxide ceramic fiber and preparation method thereof | |
| CN104530090B (en) | A kind of preparation method of pyridine derivate | |
| CN103993387B (en) | A kind of preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level | |
| Yan et al. | An efficient iron-promoted synthesis of 6 H-indolo [2, 3-b] quinolines and neocryptolepine derivatives | |
| CN104961715B (en) | A kind of preparation method of Dapagliflozin | |
| Achar et al. | Synthesis, characterization, crystal structure and antibacterial properties of N–and O–functionalized (benz) imidazolium salts and their N–heterocyclic carbene silver (I) complexes | |
| CN109896546B (en) | Preparation method of ammonium tungsten bronze nanorod | |
| Abdolmohammadi et al. | An efficient green synthesis of 3-Amino-1H-chromenes catalyzed by ZnO Nanoparticles thin-film | |
| CN107698643B (en) | A kind of preparation method of dehydroepiandros-sterone | |
| CN109384664A (en) | A kind of Ai Le replaces the preparation method of Buddhist nun's intermediate | |
| TW200505568A (en) | Phosphorus/vanadium catalyst preparation | |
| CN103980216A (en) | Synthesis method of chloridized-2,3,5-triphenyl tetrazolium chloride | |
| CN101186499A (en) | Zirconium oxide quaternary system composite ceramic material containing mullite component | |
| CN104496937A (en) | Synthetic method of 2-mercaptobenzothiazolyl-(Z)-(2-aminothiazol-4-yl)-2-(tert-butoxycarbonyl) isopropoxyiminoacetate | |
| CN101463011A (en) | Process for synthesizing 3,4-dihydropyrimidine-2-keto | |
| CN104071844A (en) | Burning method for preparing Sr2YTaO6 powder | |
| CN103664750A (en) | Synthetic method of prazole chloride | |
| CN103275153B (en) | A kind of preparation method of fidaxomicin crystal | |
| CN104370821B (en) | The preparation method and application of benzimidazoles part and dinuclear complex thereof | |
| CN102391175B (en) | The green synthesis method of 2,2 ＇-dipyridyl-4,4 ＇-dicarbaldehyde | |
| CN106518865B (en) | Preparation method of 1-alkenyl indolizine derivative | |
| CN101875640A (en) | Method for preparing pyrazinecarboxylic acid in ionic liquid | |
| Peng et al. | Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr 6 clusters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHAOXING SP HI-TECH. CO., LTD. Effective date: 20121228 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20121228 Address after: Licheng Alexander Road in Ji'nan City, Shandong province 250100 No. 27 Applicant after: Shandong University Applicant after: Shaoxing Shengnuo Ultrahigh Temperature Crystal Fibre Material Co., Ltd. Address before: Licheng Alexander Road in Ji'nan City, Shandong province 250100 No. 27 Applicant before: Shandong University |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150422 Termination date: 20180728 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |