CN101830506A - Preparation method of high-purity nano zirconium dioxide - Google Patents
Preparation method of high-purity nano zirconium dioxide Download PDFInfo
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Abstract
The invention discloses a preparation method of high-purity nano zirconium dioxide, which comprises the following steps: firstly, preparing zirconium oxychloride by using zirconite as a raw material, then preparing 0.3 to 0.5 mol/L zirconium oxychloride solution, adding 25wt% to 30wt% of NH4OH into the zirconium oxychloride solution while stirring until the pH is in the range of 9 to 9.5, precipitating after stirring uniformly, and finally obtaining the high-purity nano zirconium dioxide by the processes of washing and filtering, dehydrating wit alcohol, drying, ball milling and roasting. The preparation method uses a liquid phase precipitation method to prepare nano zirconium dioxide powder. The invention solves the problem of nano zirconium dioxide aggregation, improves surface activation grade, has the advantages of large drying treatment capacity, high safety, convenient control, low aggregation of produced powder, small granularity of powder obtained after surface treatment, uniform distribution, regular appearance, and dry and loose prepared zirconium dioxide powder, and can be widely applied to the aspects of catalysis, filtering, photoabsorption, medicine, magnetic medium, structural ceramics, new materials and the like.
Description
Technical field
The present invention relates to a kind of preparation method of zirconium dioxide, especially relate to a kind of preparation method of highly purified nano level zirconium dioxide.
Background technology
Present nano zirconium dioxide (ZrO
2) because grain size is little, surface-area is big, surface atom accounts for total atom and counts reasons such as ratio is big, therefore it has characteristics such as quantum effect, small-size effect, surface effects and macro quanta tunnel effect, make it derive the not available many special propertys of conventional solid, it is had broad application prospects at aspects such as catalysis, optical filtering, light absorption, medicine, magneticmedium, structural ceramics and novel materials.And the production of zirconium dioxide is there to be longer phase of history, existing up till now multiple preparation method, but the broad particle distribution and the height of the zirconium dioxide powder that current preparation method produces, simultaneously also exist reaction time long, power consumption is big, complex process, processing condition harshness, shortcomings such as production unit costliness are difficult for being applied in the middle of the industrial production.
Summary of the invention
Technical problem to be solved by this invention has provided a kind of preparation method of high-purity nano zirconium dioxide, this preparation method adopts liquid-phase precipitation method to prepare the nano zirconium dioxide powder, liquid-phase precipitation method is when only depositing a kind of metallic cation in the aqueous solution, and the homogeneous chemical reaction of preparation nano zirconium dioxide powder forms sedimentary method.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of high-purity nano zirconium dioxide, this preparation method is to be that raw material makes basic zirconium chloride with zircon earlier, makes 0.3～0.5mol/L zirconium oxychloride solution afterwards, under continuous stirring with the NH of 25～30wt%
4OH adds zirconium oxychloride solution, to PH9～9.5, and the postprecipitation that stirs, again through washing and filtering, pure eluting water, drying, ball milling and after calcination, make high-purity nano zirconium dioxide.
Wherein the basic zirconium chloride preparation comprises step:
Sintering gets sintered material with the zircon powder by sintering in the sodium hydroxide of 700 ℃～750 ℃ of mass ratio 1: 1.1～1.5 addings; Wherein zircon and sodium hydroxide sintering more than 700 ℃, preferred 700 ℃～750 ℃, mainly contain following reaction
ZrSiO
4+2NaOH-Na
2ZrSiO
5+H
2O
ZrSiO
4+4NaOH-Na
2ZrO
3+Na
2SiO
3+2H
2O
ZrSiO
4+6NaOH-Na
2ZrO
3+Na
4SiO
4+3H
2O
In concrete the production, it is the sodium hydroxide sheet alkali of 99wt% that sodium hydroxide can adopt content, with sodium hydroxide in container such as sintering pot, be heated to more than 700 ℃, preferred 700 ℃～750 ℃, can adopt during heating and be heated to 300～400 ℃ earlier, make more than the limpid back of the sodium hydroxide liquid level reheat to 700 ℃, homogeneous heating, add zirconium dioxide diamond stone powder afterwards, the zircon powder preferably adopts 80 orders, after material reaction is complete, cool off sintered material, reaction back Si transformation efficiency is greater than 99.5%;
Washing is pressed sintered material and water and is washed greater than 1: 6 by mass ratio, and sintered material and quality are than preferred 1: 6～8, adopt flushing against the current, the water lotion temperature is not less than 80 ℃, preferred 80 ℃～100 ℃, washing is not less than 0.5 hour, preferred 0.5～1.5 hour, filters to such an extent that washing is expected afterwards; In the sintered material in sintering reaction, sodium zirconate and water glass only are to change component and do not change composition, impurity components such as sodium and silicon are separated, and major impurity are silicon in the zircon, and after the alkali decomposition, silicon is mainly with Na
2SiO
3And Na
4SiO
4Exist, and the two is all water-soluble, and Na
2ZrO
3Water insoluble, small amount of N a
2ZrSiO
5Also water insoluble, therefore, can impurity silicon be removed by water-washing method, this has very big meaning to improving the purity of the finished product of the present invention, and this former zirconium dioxide is unexistent in producing.After this step, silica removal can reach 99wt%, and washing can be carried out in having the reactor of agitator, filters and then can adopt flame filter press.And adopt three grades of flushings against the current when sintered material is washed, and the washing fluid of each flushing removes de-iron etc. through magnetic separating device such as strong magnetic separator and carry out the next stage flushing again after assorted, the deironing rate can reach more than the 99wt%;
Remove sodium transition, adding 0.3～0.4L concentration 25wt% hydrochloric acid by 1kg washing material reacts, preferred hydrochloric acid add-on 0.35L, reaction times is more than 1 hour, preferred 1～3 hour, temperature of reaction preferred 85 ℃～100 ℃, is expected the material that must make the transition after use 1.5～2.5L water, preferred 2L water are washed and filtered by the 1kg washing after the reaction more than 85 ℃; Main component in the washing material is Na
2ZrO
3And minor N a
2ZrSiO
5, impurity such as iron, sodium, silicon and titanium, for obtaining highly purified zirconium dioxide, especially sodium must be removed, so can adopt and hydrochloric acid reaction generates water-soluble the removing of sodium-chlor mode, zirconium then can generate ZrO (OH)
2Precipitation; In this step, contains sodium composition efficient transition and can reach 99.5%, and the pH value of the sodium-chlor in the depleted filtrate is about 7 after filtering that allow compliance with emission standards can directly be discharged, and greatly reduces the pollution to water and environment.The carrying out that remove sodium this transition can carry out in having the reactor of agitator, filters and then can adopt sheet frame and filter;
Acid is decomposed, and the material that makes the transition after washing by 1kg adds 1～2kg concentration 25wt% hydrochloric acid and carries out the acid decomposition, preferably adds 1.5kg hydrochloric acid, 85 ℃～100 ℃ of reaction Heating temperatures, 5～8 hours heat-up times, afterreaction liquid acidity 7.5 ± 0.2mol/L, solid content 250g/L are decomposed in acid; Main component is ZrO (OH) in expecting transition
2With small amount of N a
2ZrSiO
5, in acid is decomposed, under the hydrochloric acid effect, react ZrO (OH)
2Generate ZrOCl with hydrochloric acid reaction
2, and Na
2ZrSiO
5Generate H with hydrochloric acid reaction
2SiO
3And ZrOCl, and sodium-chlor, wherein principal reaction is Na
2ZrSiO
5With hydrochloric acid reaction, make it deviate from silicon, be convenient to removal of impurities.And the back rate of decomposition is decomposed in acid can be greater than 99.5wt%, and product direct crystallization rate is greater than 90wt%.The carrying out that this acid is decomposed can carry out in having the reactor of agitator.
Crystallisation by cooling and water-soluble, water-soluble and filtration stoste behind the crystallisation by cooling, water-soluble aqueous solution solid content is 80g/L, acidity 3.7mol/L, the crystallisation by cooling time is not less than 36 hours, adds the crystallization flocculation agent; The purpose of this step is to adopt to extract the highly purified aqueous solution with the overcooling crystallization earlier, and Zr is separated fully with silicon, and the silicon eduction rate reaches 99.9wt%, and the crystallization flocculation agent of adding can be polyoxyethylene glycol; Filter the siliceous slag charge in back and behind washing and filtering, get the white residue product, and filtering washing lotion can be back to water-soluble operation;
Condensing crystal will filter the stoste evaporating, concentrating and crystallizing 5～7 hours, percent crystallization in massecuite＞99wt%, washing and filtering afterwards, and dehydration, get basic zirconium chloride, may command evaporating, concentrating and crystallizing temperature, by condensing crystal removal of impurities once more, impurity in the material is eliminated as much as possible, washing and filtering more afterwards, and dewater basic zirconium chloride, can adopt centrifuge dehydration, and centrifugate can be back to sour decomposition process behind the filter dehydration; Temperature fall time can be more than 15 hours, to obtain high-quality crystal when crystallization is lowered the temperature.In concrete the production, can control the acidity 4.5mol/L of stoste, ZrO
2Content 80g/L, and the acidity 6.3mol/L of crystallization material, ZrO
2Content 160g/L, the acidity 7.2mol/L of washing lotion during washing.The carrying out of this step condensing crystal can carry out in graphite evaporator, washing and filtering can carry out, dewater in enamel glass or glass still and suction filtration groove etc. adopts lining to mould whizzer.
Through the basic zirconium chloride that above-mentioned steps is produced, its index can reach: Fe
2O
3＜2PPm, TiO
2＜1PPm, SiO
2＜5PPm, Na
2O＜5PPm, turbidity＜1NTU is to be used to produce highly purified high-quality zirconium dioxide.
Adopt basic zirconium chloride to produce zirconium dioxide, basic zirconium chloride can be made 0.3～0.5mol/L zirconium oxychloride solution, under constantly stirring with the NH of 25～30wt%
4OH adds zirconium oxychloride solution, NH
4OH adopts the mode that slowly adds, and to reaction solution PH9～9.5, generates zirconium dioxide behind the postprecipitation that stirs; React completely, the zirconium transformation efficiency can reach more than the 99.5wt%, and before precipitation produces, can add molecular weight ten thousand of dispersion agent polyoxyethylene glycol more than 8000 or the relative basic zirconium chloride weight of polyvinyl alcohol/; This precipitation process can be carried out in having the agitator enamel still, and filter and pure eluting water washing of precipitate the reaction back, contains a large amount of NH in the precipitation
4Cl, must remove, the throw out filtration is washed with water to no chlorion, can adopt silver nitrate solution to carry out titration, to determine washing to the greatest extent of chlorion, use alcohol as the polyoxyethylene glycol washing again, available alcohol washing is repeatedly as three times, the water that is adsorbed on the throw out is removed, and the alcohol effect of washing is to adopt organic radical because of replacing ZrO (OH)
2The non-bridge formation hydroxyl of micelle reduces the reunion of powder in postorder drying and the calcination.The soft water temperature of water flushing usefulness can adopt 50 ℃, dehydration back water content＜2wt%; Drying, ball milling and after calcination, make high-purity nano zirconium dioxide afterwards.Again the zirconium dioxide that makes is carried out surface treatment and get the zirconium dioxide crystal grain that particle diameter is 10～50nm.Wherein drying step is to make the planar water that is attached to particle surface, organism and chemically-bonded water, under differing temps, progressively become gas phase, passing pore by self-diffusion from particle is evaporated to the surface and overflows, and remove for making the volatile matter segmentation, obtain good dispersity and porous powder, drying can adopt substep dry, for earlier 80 ℃～120 ℃ dryings, again 150 ℃～190 ℃ dryings, and 150 ℃～190 ℃ time of drying is 0.4～0.6 hour, preferred 0.5 hour, and make moisture＜0.5wt% behind the product drying after the drying, also 150 ℃～190 ℃ time of drying of may command, dry about 8～12 hours.And when drying, adopt and add the butanols azeotropic vaporization.The dry equipment that adopts can adopt the corrosion resistant drying bed.In precipitation and drying process, can form the ZrO of amorphous
2Polymer, aggregation procedure is the spontaneous process that particle surface energy reduces, in above drying process, can avoid producing hard aggregation, but soft-agglomerated then can be inevitable, dried powder is through ball milling, soft-agglomerated second particle is disperseed again, and ball milling then carries out in confined conditions with ball mill, avoids impurity to enter.Gelinite is during drying removed planar water and partial organic substances, but can not decompose hydration ZrO at low temperatures
2To remove organism and the inorganic volatile matter of staying in the soft particle of gelinite of high temperature, amorphous exsiccant hydration ZrO
2Powder calcination under 600 ℃ temperature can be with hydration ZrO
2In combination water, the ZrO that takes place in the calcination stage
2Powder ball is poly-to be because high-temperature calcination makes established coacervate generation local sintering further firmly, and in order to control the calcination quality, the control calcination temperature can not surpass 600 ℃, and preferably calcination temperature is 300～600 ℃, zirconium dioxide content＞99.9wt% after the calcination.Calcination equipment can adopt the forging steam stove.
Because ZrO
2Powder easily produces reunion, can handle it, so that store and use, can adopt surface processing equipment such as surface treating machine to ZrO
2Powder carries out surface treatment, and getting particle diameter is the ultra-fine zirconium dioxide crystal grain of 10～50nm.
The preparation method of high-purity nano zirconium dioxide of the present invention, solved the reunion of nano zirconium dioxide, comprise hard aggregation and soft-agglomerated, increased the surface active degree, made complete satisfactory high-purity nano zirconium dioxide, and it is few to have the reaction times, and the drying treatment amount is big, and is safe, equipment is simple, be convenient to control, the powder agglomeration of production is little, and the powder granularity of gained is little after the surface treatment, be evenly distributed, pattern is regular, and the loose shape of zirconium dioxide powder drying that makes can be widely used in catalysis, filter, light absorption, medicine, magneticmedium, aspect such as structural ceramics and novel material.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is further described.
Fig. 1 is preparation method's schematic diagram of high-purity nano zirconium dioxide of the present invention;
Fig. 2 is preparation method's schematic diagram of basic zirconium chloride in the high-purity nano zirconium dioxide of the present invention.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment one
As depicted in figs. 1 and 2, the preparation method of high-purity nano zirconium dioxide comprises:
1. basic zirconium chloride preparation comprises step:
Sintering is the sodium hydroxide sheet alkali of 99wt% with content, is heated to 750 ℃ in sintering pot, 80 order zircons are pressed mass ratio 1: 1.3 add in the caustic lye of soda, material reaction fully after, cool off sintered material, reaction back Si transformation efficiency is greater than 99.5%;
Washing, sintered material and water are washed by mass ratio by the back at 1: 8, adopt three grades of flushings against the current, 80 ℃ of water lotion temperature, washed 1.5 hours, and the washing fluid of each flushing removes de-iron etc. through strong magnetic separator and be used further to next stage after assorted and wash, silica removal can reach 99wt%, but more than the deironing rate 99wt%, filter to such an extent that washing is expected;
React by 1kg washing material adding 0.35L concentration 25wt% hydrochloric acid except that sodium transition, 3 hours reaction times, and 85 ℃ of temperature of reaction, reaction is afterwards by the material that must make the transition after 1kg washing material use 2L water washing and the filtration; Transition, efficient can reach 99.5%, and the pH value of the sodium-chlor in the depleted filtrate is about 7 after filtering, and allow compliance with emission standards can directly be discharged;
Acid is decomposed, and the material that makes the transition after washing by 1kg adds 1.5kg concentration 25wt% hydrochloric acid and carries out the acid decomposition, reacts 85 ℃ of Heating temperatures, 8 hours heat-up times, sour afterreaction liquid acidity 7.5 ± 0.2mol/L, the solid content 250g/L of decomposing; But back rate of decomposition 99.5wt%, product direct crystallization rate 90wt% are decomposed in acid;
Crystallisation by cooling and water-soluble, water-soluble and filtration stoste behind the crystallisation by cooling, water-soluble aqueous solution solid content is 80g/L, acidity 3.7mol/L, 36 hours crystallisation by cooling time; The silicon eduction rate reaches 99.9wt%;
Condensing crystal will filter the stoste evaporating, concentrating and crystallizing 5 hours, the acidity 4.5mol/L of stoste, ZrO
2Content 80g/L, and the acidity 6.3mol/L of crystallization material, ZrO
2Content 160g/L, percent crystallization in massecuite＞99wt%, washing and filtering afterwards, the acidity 7.2mol/L of washing lotion during washing, and dehydration, basic zirconium chloride, the basic zirconium chloride of producing, its index can reach: Fe
2O
3＜2PPm, TiO
2＜1PPm, SiO
2＜5PPm, Na
2O＜5PPm, turbidity＜1NTU is to be used to produce highly purified high-quality zirconium dioxide.
2. production zirconium dioxide,
Precipitation is made the 0.3mol/L zirconium oxychloride solution with the basic zirconium chloride that makes, under constantly stirring with the NH of 25wt%
4OH adds zirconium oxychloride solution, NH
4OH adopts the mode that slowly adds, and to reaction solution PH9～9.5, generates zirconium dioxide behind the postprecipitation that stirs; React completely, the zirconium transformation efficiency can reach more than the 99.5wt%, and before precipitation produces, can add molecular weight 8000 the relative basic zirconium chloride weight of dispersion agent polyoxyethylene glycol ten thousand/;
Washing and filtering washes the throw out filtration to no chlorion with water, and the soft water temperature of water flushing usefulness can adopt 50 ℃;
The alcohol eluting water with the polyoxyethylene glycol washing, with alcohol washing four times, removes the water that is adsorbed on the throw out again, dehydration back water content＜2wt%;
Dry cryodrying, 120 ℃ of drying temperatures, 12 hours time, high temperature drying, 190 ℃ of drying temperatures, be 0.5 hour time of drying, moisture after the drying＜0.5wt%;
The ball milling ball mill carries out in confined conditions;
Calcination temperature is 550 ℃, zirconium dioxide content＞99.9wt% after the calcination;
Surface treatment, getting particle diameter is the ultra-fine zirconium dioxide crystal grain of 30～50nm.
Embodiment two
As depicted in figs. 1 and 2, the preparation method of high-purity nano zirconium dioxide comprises:
1. basic zirconium chloride preparation comprises step:
Sintering is the sodium hydroxide sheet alkali of 99wt% with content, is heated to 700 ℃ in sintering pot, 80 order zircons are pressed mass ratio 1: 1.5 add in the caustic lye of soda, material reaction fully after, cool off sintered material, reaction back Si transformation efficiency is greater than 99.5%;
Washing, sintered material and water are washed by mass ratio by the back at 1: 7, adopt three grades of flushings against the current, 90 ℃ of water lotion temperature, washed 1 hour, and the washing fluid of each flushing removes de-iron etc. through strong magnetic separator and be used further to next stage after assorted and wash, silica removal can reach 99wt%, but more than the deironing rate 99wt%, filter to such an extent that washing is expected;
React by 1kg washing material adding 0.4L concentration 25wt% hydrochloric acid except that sodium transition, 2 hours reaction times, and 90 ℃ of temperature of reaction, reaction is afterwards by the material that must make the transition after 1kg washing material use 2.5L water washing and the filtration; Transition, efficient can reach 99.5%, and the pH value of the sodium-chlor in the depleted filtrate is about 7 after filtering, and allow compliance with emission standards can directly be discharged;
Acid is decomposed, and the material that makes the transition after washing by 1kg adds 2kg concentration 25wt% hydrochloric acid and carries out the acid decomposition, reacts 85 ℃ of Heating temperatures, 6 hours heat-up times, sour afterreaction liquid acidity 7.5 ± 0.2mol/L, the solid content 250g/L of decomposing; But back rate of decomposition 99.5wt%, product direct crystallization rate 90wt% are decomposed in acid;
Crystallisation by cooling and water-soluble, water-soluble and filtration stoste behind the crystallisation by cooling, water-soluble aqueous solution solid content is 80g/L, acidity 3.7mol/L, 40 hours crystallisation by cooling time; The silicon eduction rate reaches 99.9wt%;
Condensing crystal will filter the stoste evaporating, concentrating and crystallizing 7 hours, the acidity 4.5mol/L of stoste, ZrO
2Content 80g/L, and the acidity 6.3mol/L of crystallization material, ZrO
2Content 160g/L, percent crystallization in massecuite＞99wt%, washing and filtering afterwards, the acidity 7.2mol/L of washing lotion during washing, and dehydration, basic zirconium chloride, the basic zirconium chloride of producing, its index can reach: Fe
2O
3＜2PPm, TiO
2＜1PPm, SiO
2＜5PPm, Na
2O＜5PPm, turbidity＜1NTU is to be used to produce highly purified high-quality zirconium dioxide.
2. production zirconium dioxide,
Precipitation is made the 0.5mol/L zirconium oxychloride solution with the basic zirconium chloride that makes, under constantly stirring with the NH of 25wt%
4OH adds zirconium oxychloride solution, NH
4OH adopts the mode that slowly adds, and to reaction solution PH9.5, generates zirconium dioxide behind the postprecipitation that stirs; React completely, the zirconium transformation efficiency can reach more than the 99.5wt%, and before precipitation produces, can add molecular weight ten thousand of 8000 the relative basic zirconium chloride weight of dispersion agent polyvinyl alcohol/;
Washing and filtering washes the throw out filtration to no chlorion with water, and the soft water temperature of water flushing usefulness can adopt 50 ℃;
The alcohol eluting water is washed as polyoxyethylene glycol with alcohol again, with alcohol washing three times, the water that is adsorbed on the throw out is removed, water content＜2wt% after the dehydration;
Dry cryodrying, 80 ℃ of drying temperatures, 10 hours time, high temperature drying, 150 ℃ of drying temperatures, be 0.6 hour time of drying, moisture after the drying＜0.5wt%;
The ball milling ball mill carries out in confined conditions;
Calcination temperature is 580 ℃, zirconium dioxide content＞99.9wt% after the calcination;
Surface treatment, getting particle diameter is the ultra-fine zirconium dioxide crystal grain of 10～30nm.
Claims (7)
1. the preparation method of a high-purity nano zirconium dioxide is characterized in that: this preparation method makes basic zirconium chloride with zircon earlier, makes 0.3～0.5mol/L zirconium oxychloride solution afterwards, under constantly stirring with the NH of 25～30wt%
4OH adds zirconium oxychloride solution, to PH9～9.5, and the postprecipitation that stirs, again through washing and filtering, pure eluting water, drying, ball milling and after calcination, make high-purity nano zirconium dioxide.
2. the preparation method of high-purity nano zirconium dioxide as claimed in claim 1 is characterized in that described basic zirconium chloride preparation comprises step:
Sintering, the zircon powder added by mass ratio 1: 1.1～1.5 react completely in 700 ℃～750 ℃ the sodium hydroxide sintered material;
Wash, sintered material and water are washed by mass ratio 1: 6～8, adopt flushing against the current, 80～100 ℃ of water lotion temperature are washed and were filtered to such an extent that washing is expected in 0.5～1.5 hour afterwards;
Remove sodium transition, add 0.3～0.4L concentration 25wt% hydrochloric acid by 1kg washing material and react, 1～3 hour reaction times, 85 ℃～100 ℃ of temperature, material must make the transition after washing afterwards and filtering;
Acid is decomposed, and the material that makes the transition after washing by 1kg adds 1～2kg concentration 25wt% hydrochloric acid and carries out the acid decomposition, reacts 85 ℃～100 ℃ of Heating temperatures, 5～8 hours heat-up times, sour afterreaction liquid acidity 7.5 ± 0.2mol/L, the solid content 250g/L of decomposing;
Crystallisation by cooling and water-soluble, water-soluble and filtration stoste behind the crystallisation by cooling, aqueous solution solid content is 80g/L, acidity 3.7mol/L, crystallization flocculation agent are polyoxyethylene glycol;
Condensing crystal will filter the stoste evaporating, concentrating and crystallizing, percent crystallization in massecuite＞99wt%, and washing and filtering, and dehydration afterwards gets basic zirconium chloride.
3. the preparation method of high-purity nano zirconium dioxide as claimed in claim 2 is characterized in that: three grades of flushings are against the current adopted in described sintered material washing, and the washing fluid of each flushing carries out the next stage flushing again after the magnetic separating device removal of impurities.
4. the preparation method of high-purity nano zirconium dioxide as claimed in claim 1, it is characterized in that: the described dry substep that adopts is dry, for earlier 80 ℃～120 ℃ dryings, again 150 ℃～190 ℃ dryings, and 150 ℃～190 ℃ time of drying is 0.4～0.6 hour, moisture after the drying＜0.5wt%.
5. the preparation method of high-purity nano zirconium dioxide as claimed in claim 4 is characterized in that: adopt butanols azeotropic vaporization drying when dry.
6. the preparation method of high-purity nano zirconium dioxide as claimed in claim 1, it is characterized in that: described calcination temperature is 300～600 ℃, zirconium dioxide content＞99.9wt% after the calcination.
7. as the preparation method of each high-purity nano zirconium dioxide in the claim 1 to 6, it is characterized in that: the zirconium dioxide that makes is carried out surface treatment get the zirconium dioxide crystal grain that particle diameter is 10～50nm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260324A (en) * | 2000-01-25 | 2000-07-19 | 清华大学 | Preparation method for zirconium dioxide |
| CN1442369A (en) * | 2003-04-02 | 2003-09-17 | 广东东方锆业科技股份有限公司 | Crystallization technology in preparation of zirconium oxychloride and its crystalization equipment |
| CN1699183A (en) * | 2005-05-25 | 2005-11-23 | 宜兴新兴锆业有限公司 | Improved high grade zirconium hydroxide production process |
-
2010
- 2010-05-18 CN CN 201010174643 patent/CN101830506A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260324A (en) * | 2000-01-25 | 2000-07-19 | 清华大学 | Preparation method for zirconium dioxide |
| CN1442369A (en) * | 2003-04-02 | 2003-09-17 | 广东东方锆业科技股份有限公司 | Crystallization technology in preparation of zirconium oxychloride and its crystalization equipment |
| CN1699183A (en) * | 2005-05-25 | 2005-11-23 | 宜兴新兴锆业有限公司 | Improved high grade zirconium hydroxide production process |
Non-Patent Citations (2)
| Title |
|---|
| 《广东化工》 20021231 吴锦鹏等 氯氧化锆生产中除钠工艺的研究 7-8 1-7 , 第4期 2 * |
| 《无机盐工业》 20040531 唐勋海等 氯氧化锆前驱体制备纳米氧化锆的机理探讨 14、15、55 1-7 第36卷, 第3期 2 * |
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| CN104003438A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization of zirconium oxychloride acidolysis solution |
| CN104003438B (en) * | 2013-02-26 | 2016-04-06 | 中国科学院过程工程研究所 | The method of a kind of zirconium oxychloride acid hydrolysis solution desiliconization |
| CN103318957B (en) * | 2013-06-20 | 2015-07-15 | 淄博广通化工有限责任公司 | Special zirconium oxychloride for coated cadmium selenide red ceramic pigment and preparation method thereof |
| CN103318957A (en) * | 2013-06-20 | 2013-09-25 | 淄博广通化工有限责任公司 | Special zirconium oxychloride for coated cadmium selenide red ceramic pigment and preparation method thereof |
| CN103523830A (en) * | 2013-10-29 | 2014-01-22 | 神华集团有限责任公司 | High-specific-surface area pure-monoclinic-phase zirconia preparation method |
| CN104787802A (en) * | 2015-05-04 | 2015-07-22 | 内蒙古工业大学 | Preparation method of controllable-shape nano zirconium oxide |
| CN104787802B (en) * | 2015-05-04 | 2016-07-27 | 内蒙古工业大学 | The nano zircite preparation method of morphology controllable |
| CN105084417A (en) * | 2015-09-30 | 2015-11-25 | 山西晶科光电材料有限公司 | Preparation method of high-purity cubic zirconia fine particles for insulating layer of sapphire furnace |
| CN106766676A (en) * | 2016-12-20 | 2017-05-31 | 西北稀有金属材料研究院 | A kind of drying means of tin oxide precursor powder |
| CN107055609A (en) * | 2016-12-29 | 2017-08-18 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
| CN107055609B (en) * | 2016-12-29 | 2018-06-08 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
| CN115161784A (en) * | 2022-06-23 | 2022-10-11 | 东华大学 | Method for large-scale production of continuous ceramic filaments |
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