CN103708549A - Preparation method of nanoscale ZrO2 powder - Google Patents

Preparation method of nanoscale ZrO2 powder Download PDF

Info

Publication number
CN103708549A
CN103708549A CN201410004827.XA CN201410004827A CN103708549A CN 103708549 A CN103708549 A CN 103708549A CN 201410004827 A CN201410004827 A CN 201410004827A CN 103708549 A CN103708549 A CN 103708549A
Authority
CN
China
Prior art keywords
zrf
zro
gaseous state
mixture
solid
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
Application number
CN201410004827.XA
Other languages
Chinese (zh)
Other versions
CN103708549B (en
Inventor
龚亚云
刘瑞
林乐洪
章林
李丹阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUIZHOU WANFANG ALUMINUM SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
Original Assignee
GUIZHOU WANFANG ALUMINUM SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by GUIZHOU WANFANG ALUMINUM SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd filed Critical GUIZHOU WANFANG ALUMINUM SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
Priority to CN201410004827.XA priority Critical patent/CN103708549B/en
Publication of CN103708549A publication Critical patent/CN103708549A/en
Application granted granted Critical
Publication of CN103708549B publication Critical patent/CN103708549B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention relates to the field of preparation of chemical materials and particularly relates to a preparation method of nanoscale ZrO2 powder. The preparation method of the nanoscale ZrO2 powder comprises the following steps: mixing ZrO2-containing minerals or Zr-containing minerals and fluoride to obtain a mixture; enabling the mixture to react to finally obtain gaseous ZrF4; introducing water vapor to the gaseous ZrF4, and hydrolyzing to obtain a gas-solid mixture of solid ZrO2 and gaseous HF; carrying out shock cooling on the gas-solid mixture for crystalizing at 200-450 DEG C to obtain the nanoscale ZrO2 powder. According to the preparation method of the nanoscale ZrO2 powder, the preparation process can be finished by adopting a well-known reaction device in the field, and the production process and steps are simplified; in addition, cheap ZrO2-containing minerals or Zr-containing minerals, the fluoride and the water vapor are adopted as main raw materials, so that the production cost is low.

Description

Nano level ZrO 2the preparation method of powder
Technical field
The present invention relates to chemical materials preparation field, in particular to nano level ZrO 2the preparation method of powder.
Background technology
ZrO 2for white crystalline powder, it has high-melting-point, high boiling point, thermal conductivity is little, thermal expansivity is large, frictional coefficient is low, wear resistance is good, chemical stability is high, good characteristics such as etch resistant properties (ability especially with good chemical resistance of concrete and microbial attack), is ideal high-temperature refractory, abrasive substance and high temperature insulating material.In many different fields, such as beramic color, engineering ceramics, jewel industry, piezoelectric element, ion-exchanger and solid electrolyte etc., all tool has been widely used.From structure, ZrO 2owing to thering is acid and basic surface center, because of but a kind of desirable acidic group double-function catalyzing material.In addition, ZrO 2also have unique transformation toughening, this makes ZrO 2pottery not only intensity is high, and fracture toughness property is also very large.Meanwhile, ZrO 2also there is high temperature oxygen ionic conductivity, therefore be also widely used in oxygen sensor.High pure and ultra-fine ZrO 2can be for high-tech sector, as wire-drawing die, cutter, fine grinding bar, unlubricated spot contact bearing etc.
In correlation technique, preparation ZrO 2method mainly contain following several method: solid-phase synthesis, to ZrO 2in raw material, add a certain proportion of stablizer (CaO, MgO, CeO 2), the fine powder of wet-milling to 2 μ m in ball mill by raw material and stablizer, drying, beats powder, makes agglomerate, and at 1700 ℃, calcining, obtains ZrO 2.Normal-temperature water solution, soon salts solution (such as the ZrOCl of high purity zirconium 2) add deionized water hydrolysis, and boil for a long time the salts solution of zirconium, hydrolysis reaction carries out more than 50h, refiltering under boiling, with deionized water, washes, is dried, calcines pulverizing, makes ZrO 2.Flame hydrolysis, soon salts solution (such as the ZrOCl of high purity zirconium 2) to spray into temperature be in the decomposing furnace of 1000 ℃, the moisture evaporation in the salts solution drop of small zirconium, hydrolysis generates ZrO 2, the ZrO after hydrolysis 2through cyclonic separator, collect, then through pickling, washing, oven dry, make ZrO 2.Organometallics hydrolysis method, is about to be dissolved in high purity organic solvent containing zirconium organometallics, meets water decomposition, preparation ZrO 2.High-temperature spray pyrolysis method, is about to spraying dry and decompose synthesis technique and combine, with solvent by ZrO 2raw material wiring solution-forming, then, by solution atomization and import in reactor, volatilizees rapidly solution by spraying plant, reactant generation thermolysis, preparation ZrO 2.Spraying induction coupling Plasma pyrolysis, with solvent by ZrO 2raw material wiring solution-forming, sends into solution atomization in plasma tail flame by spraying plant, makes it that pyrolytic reaction occur, preparation ZrO 2.
To sum up, solid-phase synthesis and high-temperature spray pyrolysis method processing step are many; Normal-temperature water solution, flame hydrolysis and organometallics hydrolysis method raw materials cost are high; Spraying induction coupling Plasma pyrolysis production unit cost is high.Therefore in correlation technique, ZrO 2production craft step is various, and production cost is high.
Summary of the invention
The object of the present invention is to provide nano level ZrO 2the preparation method of powder, to solve the above problems.
Nano level ZrO is provided in an embodiment of the present invention 2the preparation method of powder, comprises the steps:
Will be containing ZrO 2mineral or and mix with fluorochemical containing zirconium ore thing, obtain mixture;
Mixture is reacted, and finally obtain gaseous state ZrF 4;
To gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2gas-solid mixture with gaseous state HF;
By 200 ℃～450 ℃ crystallizations of gas-solid mixture quenching, obtain nano level ZrO 2powder.
Furthermore, containing zirconium ore thing, mix with fluorochemical, obtain mixture; And while containing silicon matter in containing zirconium ore thing, step is reacted mixture, and finally obtains gaseous state ZrF 4, also obtain gaseous state SiF 4; Step is reacted mixture, and finally obtains gaseous state ZrF 4with step to gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2and between the gas-solid mixture of gaseous state HF, also comprise the steps:
By gaseous state ZrF 4with gaseous state SiF 4the mixed gas forming is cooled to below 600 ℃, obtains solid-state ZrF 4with gaseous state SiF 4gas-solid mixture;
Gas-solid mixture is carried out to separation, obtain solid-state ZrF 4;
By solid-state ZrF 4be warming up to more than 1000 ℃, gasification, obtains gaseous state ZrF 4.
Preferably, in step to gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2in the gas-solid mixture of gaseous state HF, gaseous state ZrF 4in the mixed gas forming with water vapour, the volumn concentration of water vapour is 30%～80%; Hydrolysis temperature is at least 1000 ℃.
Preferably, in step, by 200 ℃～450 ℃ crystallizations of gas-solid mixture quenching, obtain nano level ZrO 2in powder, the speed of quenching is 50 ℃/min～200 ℃/min.
Preferably, in step, by 200 ℃～450 ℃ crystallizations of gas-solid mixture quenching, obtain nano level ZrO 2after powder, also comprise the steps:
To nano level ZrO 2powder is assembled, separated, depickling processing.
Furthermore, obtain gaseous state ZrF 4with step to gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2and between gaseous state HF mixed gas, also comprise the steps:
To gaseous state ZrF 4carry out purification process.
Preferably, step by containing the mineral of ZrO2 or and containing zirconium ore thing, mix with fluorochemical, obtain in mixture, when fluorochemical is a kind of in following several material: NaF, NH 4f, NH 4hF 2, CaF 2, AlF 3; Containing the mineral of ZrO2 or and containing the particle diameter of zirconium ore thing and fluorochemical, be all less than 3mm; In mixture, the quality percentage composition of fluorochemical is 10%～90%;
When fluorochemical is hydrofluoric acid, the mass concentration of hydrofluoric acid is 20%～40%, and in mixture, the massfraction of hydrofluoric acid is 10%～90%.
Preferably, described fluorochemical is a kind of in following several material: NaF, NH 4f, NH 4hF 2, CaF 2, AlF 3; Make mixture reaction, and finally obtain gaseous state ZrF 4concrete steps be:
Mixture is calcined 1 hour～12 hours at 910 ℃～1200 ℃, obtained gaseous state ZrF 4.
Preferably, fluorochemical is hydrofluoric acid, and step makes mixture reaction, and finally obtains gaseous state ZrF 4concrete steps be:
Make mixture 100 ℃～200 ℃ reactions 3 hours～15 hours, generate solid-state ZrF 4;
By solid-state ZrF 4be heated to gaseous state, obtain gaseous state ZrF 4.
Preferably, containing ZrO 2mineral or containing zirconium ore thing, be a kind of in following several material: baddeleyite, zircon, zirkelite, containing ZrO 2waste material.
The nano level ZrO of the above embodiment of the present invention 2the preparation method of powder, can adopt reaction unit well known in the art to complete preparation process, and production craft step is simplified; And adopt the cheap mineral containing ZrO2 or and containing zirconium ore thing, fluorochemical and water vapour, be main raw material, production cost is low.
Embodiment
Below by specific embodiment, the present invention is described in further detail.
Embodiments of the invention provide nano level ZrO 2the preparation method of powder, comprises the steps:
Step 101: by containing the mineral of ZrO2 or and containing zirconium ore thing, mix with fluorochemical, obtain mixture;
Step 102: make mixture reaction, and finally obtain gaseous state ZrF 4;
Step 103: to gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2gas-solid mixture with gaseous state HF;
Step 104: by 200 ℃～450 ℃ crystallizations of gas-solid mixture quenching, obtain nano level ZrO 2powder.
The nano level ZrO providing in the embodiment of the present invention 2in the preparation method of powder, utilize fluorochemical (AF z) in F element with containing the mineral of ZrO2 or and containing zirconium ore thing (M xo ynZrO 2) in close fluorine element Zr react, its reaction formula is:
M xO y·nZrO 2+AF z→M xO y+A 2O z+ZrF4
ZrF 4+2H 2O→ZrO 2+4HF
By above-mentioned reaction, generate high-purity ZrF of gaseous state 4.Utilize ZrF 4make and contain highly purified gaseous state ZrO with water vapor generation pyrohydrolysis 2mixed gas with gaseous state HF.By by mixed gas quenching to 200 ℃～450 ℃ of crystallizations, obtain nano level ZrO 2powder.The nano level ZrO that the present embodiment provides 2the preparation method of powder, production craft step is simplified, and adopts the cheap ZrO that contains 2mineral or and containing zirconium ore thing, fluorochemical and water vapour, be main raw material, therefore production cost is low.Nano level ZrO prepared by the preparation method who provides by the present embodiment in addition, 2powder, its crystal particle diameter little (being controlled at 5nm～500nm), nano level ZrO 2powder distribution is even, there is no impurity, and coacervate is few, and sintering character is strong; And require low to reaction conditions and conversion unit.
If contain silicon matter containing in zirconium ore thing, because silicon matter also can react with fluorochemical, generate gaseous state SiF 4, as the SiF generating 4when gas enters hydrolyzation system, can be hydrolyzed, generate solid SiO 2, this part SiO 2can be on the purity of nanometer ZrO2 powder be brought to fatal impact.Therefore in step 102, also can generate gaseous state SiF 4, obtain gaseous state ZrF 4with gaseous state SiF 4mixed gas.In order to improve the ZrO of final preparation 2the purity of powder, therefore between step 102 and step 103, also comprise the steps:
Step 1021: by gaseous state ZrF 4with gaseous state SiF 4the mixed gas forming is cooled to below 600 ℃, obtains solid-state ZrF 4with gaseous state SiF 4gas-solid mixture;
Step 1022: gas-solid mixture is carried out to separation, obtain solid-state ZrF 4;
Step 1023: by solid-state ZrF 4be warming up to more than 1000 ℃, gasification, obtains gaseous state ZrF 4.
In order better to control nano level ZrO 2the particle diameter of powder, preferably, in step 103, gaseous state ZrF 4in the mixed gas forming with water vapour, the volumn concentration of water vapour is 30%～80%; Hydrolysis temperature is at least 1000 ℃.
In step 104, the speed of quenching is 50 ℃/min～200 ℃/min.
By the control to the temperature of the intake of water vapour, hydrolysis reaction and quenching speed, can better control ZrO 2nucleation and growth speed, make final ZrO 2the particle diameter of powder can be controlled in the scope of 5nm～500nm.
In order to improve the purity of the finished product, preferably, after step 104, further comprise the following steps:
Step 105: to nano level ZrO 2powder is assembled, separated, depickling processing.
In order further to improve the nano level ZrO of final preparation 2productive rate and purity, therefore preferably, between step 102 and step 103 or between step 1023 and step 103, further comprise the steps:
Step 106: to gaseous state ZrF 4carry out purification process.
For further cost-saving, fluorochemical is a kind of in following several material: NaF, NH 4f, NH 4hF 2, CaF 2, AlF 3; Containing the mineral of ZrO2 or and be all less than 3mm containing the particle diameter of zirconium ore thing and fluorochemical.
NaF, NH 4f, NH 4hF 2, CaF 2and AlF 3be solid, by controlling particle diameter below 3mm, can make two kinds of raw materials mix by composition, make to react carry out more complete.Wherein, when fluorochemical is NH 4f or NH 4hF 2time; Its with containing the mineral of ZrO2 or and containing zirconium ore thing, react after may generate NH 3gas, NH 3gas can be along with gaseous state ZrF 4enter together subsequent handling, and may be to nano level ZrO 2the particle diameter of powder impacts.Therefore effectively remove NH by step 106 3gas, what deserves to be explained is, the purification process in step 106 can be any known technology in this area.
When fluorochemical is that solid fluoride (is NaF, NH 4f, NH 4hF 2, CaF 2, AlF 3in a kind of) time, by containing ZrO 2mineral or and containing zirconium ore thing and fluorochemical, be mixed to form in mixture, the quality percentage composition of fluorochemical is preferably 10%～90%.Can make like this reaction more complete, contribute to improve productive rate.
In addition, when fluorochemical is solid fluoride, can adopt the mode that improves temperature of reaction directly to generate gaseous state ZrF 4, particularly, step 102 is preferably:
Mixture is calcined 1 hour～12 hours at 910 ℃～1200 ℃, obtained gaseous state ZrF 4.
If temperature, lower than 910 ℃, possibly cannot generate the ZrF of gaseous state 4if temperature, higher than 1200 ℃, may generate more by product, causes reduction ultimate yield.
But, while containing silicon-dioxide in containing zirconium ore thing, must be to ZrF 4take off SiO 4process, method is: to gaseous state ZrF 4with gaseous state SiO 4mixed gas be cooled to below 600 ℃, obtain solid-state ZrF 4with gaseous state SiO 4gas-solid mixture; Gas-solid mixture is carried out to gas solid separation and obtain solid-state ZrF 4.Then by solid-state ZrF 4be warming up to 1000 ℃ and gasify above, obtain gaseous state ZrF 4.
Fluorochemical can also be hydrofluoric acid; In raw material mixing process, containing ZrO 2mineral or and containing in zirconium ore thing and hydrofluoric acid mixing process, if directly temperature is risen within the scope of 910 ℃～1200 ℃, can cause reaction not exclusively, productive rate decline.In order to improve productive rate, preferably, step 102 preferably includes following steps:
Make mixture 100 ℃～200 ℃ reactions 3 hours～15 hours, generate solid-state ZrF 4;
By solid-state ZrF 4be heated to gaseous state, obtain gaseous state ZrF 4.
Can make like this reaction more complete, improve productive rate.
In order to make reaction more complete, the mass concentration of hydrofluoric acid is preferably 20%～40%; The massfraction of the hydrofluoric acid in described mixture is preferably 10%～90%.
In the present embodiment, in order further to reduce production costs, containing the mineral of ZrO2 or and containing zirconium ore thing, be preferably in following several material a kind of: baddeleyite, zircon, zirkelite, containing ZrO 2waste material.These raw materials easily obtain, and cost is lower.
Be below nano level ZrO provided by the invention 2the concrete preparation example of powder preparation method:
Preparation example 1: with ZrO 2waste material and NH 4f is that raw material is prepared nano level ZrO 2powder
By ZrO 2waste material in coarse particles ZrO 2and NH 4f mixes and obtains mixture, coarse particles ZrO 2with NH 4the particle diameter of F is below 3mm.NH in mixture 4the mass percent of F is 30%.Mixture, the temperature lower calcination of 910 ℃ 3 hours, is generated to NH 3, H 2o and ZrF 4.ZrF 4under high temperature, be gaseous state, overflow.By the ZrF overflowing 4after purified processing, (remove NH 3) introduce in another reactor, and passing into water vapour, the volume content of water vapour is 80%, at 910 ℃, after hydrolysis, generates ZrO 2with HF gas.The quenching to 350 ℃ of high-temperature gas mixture body obtains ZrO 2particle, rate of cooling is 50 ℃/min.Particle obtains ZrO through aftertreatment technologys such as overbunching, separation, depicklings 2powder (particle diameter is 50nm～86nm).Its reaction equation is as follows:
ZrO 2+4NH 4F→ZrF 4+4NH 3+2H 2O
ZrF 4+2H 2O→ZrO 2+4HF
Preparation example 2: with baddeleyite and AlF 3for raw material is prepared nano level ZrO 2powder
By baddeleyite and AlF 3mix and obtain mixture, baddeleyite and AlF 3particle diameter be below 3mm.AlF in mixture 3mass percent be 40%.Mixture, the temperature lower calcination of 1000 ℃ 5 hours, is generated to Al 2o 3and ZrF 4, owing to containing silicon in these mineral, so have SiO 4gas generates, so need to remove gaseous state SiO 4.To gaseous state SiO 4with gaseous state ZrF 4the mixed gas forming is cooled to below 600 ℃, obtains solid-state ZrF 4with gaseous state SiO 4gas-solid mixture, gas-solid mixture is carried out to gas solid separation and obtains solid-state ZrF 4.Then by solid-state ZrF 4be warming up to 1000 ℃ and gasify above, obtain gaseous state ZrF 4.ZrF 4under high temperature, be gaseous state, from solid, overflow.By the ZrF overflowing 4after purified processing, introduce in another reactor, and pass into water vapour, the volume content of water vapour is 60%, generates ZrO at more than 1000 ℃ temperature after hydrolysis 2with HF gas.The quenching to 450 ℃ of high-temperature gas mixture body obtains ZrO 2particle, rate of cooling is 100 ℃/min.Particle obtains ZrO through aftertreatment technologys such as overbunching, separation, depicklings 2powder (particle diameter is 20nm～47nm).Reaction equation is as follows:
3ZrO 2+4AlF 3·3H 2O→2Al 2O 3+3ZrF 4+12H 2O
ZrF 4+2H 2O→ZrO 2+4HF
Preparation example 3: with zircon and NH 4hF 2for raw material is prepared nano level ZrO 2powder
By zircon and NH 4hF 2mix and obtain mixture, zircon and NH 4hF 2particle diameter be below 3mm.NH in mixture 4hF 2mass percent be 60%.Mixture, the temperature lower calcination of 1200 ℃ 12 hours, is generated to NH 3, H 2o and ZrF 4, owing to containing silicon in these mineral, so have SiO 4gas generates, so need to remove SiO 4.To gaseous state SiO 4with gaseous state ZrF 4the mixed gas forming is cooled to below 600 ℃, obtains solid-state ZrF 4with gaseous state SiO 4gas-solid mixture, gas-solid mixture is carried out to gas solid separation and obtains solid-state ZrF 4.Then by solid-state ZrF 4be warming up to 1000 ℃ and gasify above, obtain gaseous state ZrF 4.ZrF 4under high temperature, be gaseous state, overflow.By the ZrF overflowing 4after purified processing, introduce in another reactor, and pass into water vapour, the volume content of water vapour is 40%, after 1100 ℃ of hydrolysis, generates ZrO 2with HF gas.The quenching to 350 ℃ of high-temperature gas mixture body obtains ZrO 2particle, rate of cooling is 200 ℃/min.Particle obtains ZrO through aftertreatment technologys such as overbunching, separation, depicklings 2powder (particle diameter is 33nm～56nm).Reaction equation is as follows:
ZrO 2+2NH 4HF 2→ZrF 4+2NH 3+2H 2O
ZrF 4+2H 2O→ZrO 2+4HF
Preparation example 4: with zircon sand and CaF 2for raw material is prepared fine grain size ZrO 2powder
By zircon sand and CaF 2mix and obtain mixture, zircon sand and CaF 2particle diameter be below 3mm.CaF in mixture 2mass percent be 80%.Mixture, the temperature lower calcination of 1200 ℃ 1 hour, is generated to CaO and ZrF 4, owing to containing silicon in these mineral, so have SiO 4gas generates, so need to remove SiO 4.To gaseous state SiO 4with gaseous state ZrF 4the mixed gas forming is cooled to below 600 ℃, obtains solid-state ZrF 4with gaseous state SiO 4gas-solid mixture, gas-solid mixture is carried out to gas solid separation and obtains solid-state ZrF 4.Then by solid-state ZrF 4be warming up to 1000 ℃ and gasify above, obtain gaseous state ZrF 4.ZrF 4under high temperature, be gaseous state, from solid, overflow.By the ZrF overflowing 4after purified processing, introduce in another reactor, and pass into water vapour, the volume content of water vapour is 30%, generates ZrO at more than 1000 ℃ temperature after hydrolysis 2with HF gas.The quenching to 300 ℃ of high-temperature gas mixture body obtains ZrO 2particle, rate of cooling is 150 ℃/min.Particle obtains ZrO through aftertreatment technologys such as overbunching, separation, depicklings 2powder (particle diameter is 40nm～60nm).Reaction equation is as follows:
ZrO 2+2CaF 2→ZrF 4+2CaO
ZrF 4+2H 2O→ZrO 2+4HF
Preparation example 5: take zircon and hydrofluoric acid prepares nano level ZrO as raw material 2powder
Zircon and hydrofluoric acid are mixed and obtains mixture, and the particle diameter of zircon is below 3mm.The mass concentration of hydrofluoric acid is 20%.In mixture, the massfraction of hydrofluoric acid is 60%.Mixture is reacted to 6h under the condition of 200 ℃, generate H 2o and solid-state ZrF 4, by solid-state ZrF 4910 ℃ of high temperature are heated to gaseous state, overflow.By the ZrF overflowing 4introduce in another reactor, and pass into water vapour, the volume content of water vapour is 50%, makes water vapour and gaseous state ZrF at 1200 ℃ 4hydrolysis, generates ZrO 2with HF gas.The quenching to 200 ℃ of high-temperature gas mixture body obtains ZrO 2particle, rate of cooling is 150 ℃/min.Particle obtains ZrO through aftertreatment technologys such as collection, separation, depicklings 2powder (particle diameter is 50nm～90nm).Reaction equation is as follows:
ZrO 2+4HF→ZrF 4+2H 2O
ZrF 4+2H 2O→ZrO 2+4HF
Preparation example 6: take zircon sand and hydrofluoric acid prepares nano level ZrO as raw material 2powder
Zircon sand and hydrofluoric acid are mixed and obtains mixture, and the particle diameter of zircon sand is below 3mm.The mass concentration of hydrofluoric acid is 40%.In mixture, the massfraction of hydrofluoric acid is 50%.Mixture is reacted to 10h under the condition of 100 ℃, generate H 2o and solid-state ZrF 4.By solid-state ZrF 4at 910 ℃, be heated to gaseous state, overflow.By the ZrF overflowing 4introduce in another reactor, and pass into water vapour, the volume content of water vapour is 70%, makes water vapour and gaseous state ZrF at the temperature of 1300 ℃ 4hydrolysis, generates ZrO 2with HF gas.The quenching to 250 ℃ of high-temperature gas mixture body obtains ZrO 2particle, rate of cooling is 200 ℃/min.Particle obtains ZrO through aftertreatment technologys such as collection, separation, depicklings 2powder (particle diameter is 30nm～72nm).Reaction equation is as follows:
ZrO 2+4HF→ZrF 4+2H 2O
ZrF 4+2H 2O→ZrO 2+4HF
Below in prior art, prepare ZrO 2the comparative example of powder:
Following table is the data synopsis of data and the comparative example of preparation example 1-preparation example 6:
Figure BDA0000453772970000111
Figure BDA0000453772970000121
By upper table, can find out nano level ZrO provided by the invention 2preparation method there is low cost, high quality, high yield, high purity texts.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. nano level ZrO 2the preparation method of powder, is characterized in that, comprises the steps:
Will be containing ZrO 2mineral or mix with fluorochemical containing zirconium ore thing, obtain mixture;
Described mixture is reacted, and finally obtain gaseous state ZrF 4;
To described gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2gas-solid mixture with gaseous state HF;
By 200 ℃～450 ℃ crystallizations of described gas-solid mixture quenching, obtain nano level ZrO 2powder.
2. nano level ZrO according to claim 1 2the preparation method of powder, is characterized in that, the described zirconium ore thing that contains mixes with fluorochemical, obtains mixture; And when containing silicon matter in zirconium ore thing, described step is reacted described mixture, and finally obtains gaseous state ZrF when described 4, also obtain gaseous state SiF 4; Described step is reacted described mixture, and finally obtains gaseous state ZrF 4with described step to described gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2and between the gas-solid mixture of gaseous state HF, also comprise the steps:
By described gaseous state ZrF 4with gaseous state SiF 4the mixed gas forming is cooled to below 600 ℃, obtains solid-state ZrF 4with gaseous state SiF 4gas-solid mixture;
Described gas-solid mixture is carried out to separation, obtain described solid-state ZrF 4;
By described solid-state ZrF 4be warming up to more than 1000 ℃, gasification, obtains described gaseous state ZrF 4.
3. nano level ZrO according to claim 1 2the preparation method of powder, is characterized in that, in described step to described gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2in the gas-solid mixture of gaseous state HF, described gaseous state ZrF 4in the mixed gas forming with described water vapour, the volumn concentration of described water vapour is 30%～80%; Hydrolysis temperature is at least 1000 ℃.
4. nano level ZrO according to claim 1 2the preparation method of powder, is characterized in that, in described step, by 200 ℃～450 ℃ crystallizations of described gas-solid mixture quenching, obtains nano level ZrO 2in powder, the speed of described quenching is 50 ℃/min～200 ℃/min.
5. nano level ZrO according to claim 1 2the preparation method of powder, is characterized in that, in described step, by 200 ℃～450 ℃ crystallizations of described gas-solid mixture quenching, obtains nano level ZrO 2after powder, also comprise the steps:
To described nano level ZrO 2powder is assembled, separated, depickling processing.
6. nano level ZrO according to claim 1 and 2 2the preparation method of powder, is characterized in that, obtains gaseous state ZrF 4with described step to described gaseous state ZrF 4in pass into water vapour, be hydrolyzed, obtain solid-state ZrO 2and between gaseous state HF gas-solid mixture, also comprise the steps:
To described gaseous state ZrF 4carry out purification process.
7. nano level ZrO according to claim 1 2the preparation method of powder, is characterized in that, will be containing ZrO in described step 2mineral or and mix with fluorochemical containing zirconium ore thing, obtain in mixture, when described fluorochemical is a kind of in following several material: NaF, NH 4f, NH 4hF 2, CaF 2, AlF 3; Described containing ZrO 2mineral or containing the particle diameter of zirconium ore thing and described fluorochemical, be all less than 3mm; In described mixture, the quality percentage composition of described fluorochemical is 10%～90%;
When described fluorochemical is hydrofluoric acid, the mass concentration of described hydrofluoric acid is 20%～40%, and in described mixture, the massfraction of described hydrofluoric acid is 10%～90%.
8. nano level ZrO according to claim 7 2the preparation method of powder, is characterized in that, described fluorochemical is a kind of in following several material: NaF, NH 4f, NH 4hF 2, CaF 2, AlF 3, described step makes described mixture reaction, and finally obtains gaseous state ZrF 4concrete steps be:
Described mixture is calcined 1 hour～12 hours at 910 ℃～1200 ℃, obtained gaseous state ZrF 4.
9. nano level ZrO according to claim 7 2the preparation method of powder, is characterized in that, when described fluorochemical is hydrofluoric acid, described step makes described mixture reaction, and finally obtains gaseous state ZrF 4concrete steps be:
Make described mixture 100 ℃～200 ℃ reactions 3 hours～15 hours, generate solid-state ZrF 4;
By described solid-state ZrF 4be heated to gaseous state, obtain described gaseous state ZrF 4.
10. nano level ZrO according to claim 1 2the preparation method of powder, is characterized in that, described containing ZrO 2mineral or containing zirconium ore thing, be a kind of in following several material: baddeleyite, zircon, zirkelite, containing ZrO 2waste material.
CN201410004827.XA 2014-01-06 2014-01-06 Nano level ZrO 2the preparation method of powder Active CN103708549B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410004827.XA CN103708549B (en) 2014-01-06 2014-01-06 Nano level ZrO 2the preparation method of powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410004827.XA CN103708549B (en) 2014-01-06 2014-01-06 Nano level ZrO 2the preparation method of powder

Publications (2)

Publication Number Publication Date
CN103708549A true CN103708549A (en) 2014-04-09
CN103708549B CN103708549B (en) 2015-09-16

Family

ID=50401952

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410004827.XA Active CN103708549B (en) 2014-01-06 2014-01-06 Nano level ZrO 2the preparation method of powder

Country Status (1)

Country Link
CN (1) CN103708549B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104445397A (en) * 2014-12-05 2015-03-25 三祥新材股份有限公司 Preparation method of electrofused zirconium oxide
CN109205669A (en) * 2018-11-19 2019-01-15 新特能源股份有限公司 The combined preparation process of zirconium chloride and ocratation

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US824579A (en) * 1901-11-01 1906-06-26 John W Paul Type-writer.
US2639218A (en) * 1950-09-13 1953-05-19 Dow Chemical Co Production of anhydrous zirconium fluoride
JPS58174535A (en) * 1982-04-07 1983-10-13 Hashimoto Kasei Kogyo Kk Manufacture of aluminum-zirconium mother alloy
IL64453A (en) * 1981-12-04 1985-08-30 Simcha Harel Production of zirconia from potassium zirconium fluoride
US4578252A (en) * 1985-05-14 1986-03-25 Hughes Aircraft Company Method for preparing ultra-pure zirconium and hafnium tetrafluorides
EP0370480A1 (en) * 1988-11-23 1990-05-30 Air Products And Chemicals, Inc. Process for the production of high purity zirconium tetrafluoride and other fluorides
JPH05170445A (en) * 1991-12-24 1993-07-09 Nikko Kyodo Co Ltd Production for zirconium fluoride
CN1110959A (en) * 1994-01-31 1995-11-01 南非原子能有限公司 Treatment of a chemical
CN1168658A (en) * 1994-12-02 1997-12-24 南非原子能有限公司 Treatment of a chemical article
CN101351408A (en) * 2005-06-30 2009-01-21 欧洲塞扎斯“锆”公司 Method for recycling zirconium tetrafluoride to form zirconia
CN102625779A (en) * 2009-07-29 2012-08-01 南非核能源有限公司 Treatment of zirconia-based material with ammonium bi-fluoride

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US824579A (en) * 1901-11-01 1906-06-26 John W Paul Type-writer.
US2639218A (en) * 1950-09-13 1953-05-19 Dow Chemical Co Production of anhydrous zirconium fluoride
IL64453A (en) * 1981-12-04 1985-08-30 Simcha Harel Production of zirconia from potassium zirconium fluoride
JPS58174535A (en) * 1982-04-07 1983-10-13 Hashimoto Kasei Kogyo Kk Manufacture of aluminum-zirconium mother alloy
US4578252A (en) * 1985-05-14 1986-03-25 Hughes Aircraft Company Method for preparing ultra-pure zirconium and hafnium tetrafluorides
EP0370480A1 (en) * 1988-11-23 1990-05-30 Air Products And Chemicals, Inc. Process for the production of high purity zirconium tetrafluoride and other fluorides
JPH05170445A (en) * 1991-12-24 1993-07-09 Nikko Kyodo Co Ltd Production for zirconium fluoride
CN1110959A (en) * 1994-01-31 1995-11-01 南非原子能有限公司 Treatment of a chemical
CN1168658A (en) * 1994-12-02 1997-12-24 南非原子能有限公司 Treatment of a chemical article
CN101351408A (en) * 2005-06-30 2009-01-21 欧洲塞扎斯“锆”公司 Method for recycling zirconium tetrafluoride to form zirconia
CN102625779A (en) * 2009-07-29 2012-08-01 南非核能源有限公司 Treatment of zirconia-based material with ammonium bi-fluoride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DONG FANG ET AL.: "Fabrication parameter-dependent morphologies of self-organized ZrO2 nanotubes during anodization", 《J SOLID STATE ELECTROCHEM》, vol. 16, 9 August 2011 (2011-08-09), pages 1219 - 1228 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104445397A (en) * 2014-12-05 2015-03-25 三祥新材股份有限公司 Preparation method of electrofused zirconium oxide
CN104445397B (en) * 2014-12-05 2016-06-15 三祥新材股份有限公司 A kind of preparation method of electric-melting zirconia
CN109205669A (en) * 2018-11-19 2019-01-15 新特能源股份有限公司 The combined preparation process of zirconium chloride and ocratation

Also Published As

Publication number Publication date
CN103708549B (en) 2015-09-16

Similar Documents

Publication Publication Date Title
CN100503450C (en) Method for preparing powder of zirconium oxide in high purity
CN108675327B (en) Preparation method of low-sodium submicron calcined alumina
CN101024514A (en) Novel process for preparing cubic-phase nano zirconium dioxide
CN104328478A (en) Preparation method of SiC crystal whisker
CN106629732B (en) A kind of preparation method of nanometer of ZrC-SiC composite granule
CN103588246A (en) Preparation process for nano zirconia powder
Wang et al. The environmental sustainability of synthetic wollastonite using waste from zirconium oxychloride production
CN101417815B (en) Method for preparing titanium white by spray hydrolysis
CN103708549B (en) Nano level ZrO 2the preparation method of powder
Septawendar et al. A low-cost, facile method on production of nano zirconia and silica from local zircon in a large scale using a sodium carbonate sintering technology
CN103318954B (en) Method for preparing sodium trititanate nanorods through solid-phase chemical reaction
CN1016413B (en) Process for manufacture of zirconium oxide hydrate from granular crystallized zirconium oxide
CN106946290B (en) A kind of method of vanadic anhydride purification
CN100465096C (en) Method for preparing sheet alumina using coal series kaolin rock or flyash as raw material
CN103754931B (en) TiO 2the preparation method of powder
CN103539203B (en) Method for preparing zirconium dioxide from zirconium-containing solid waste
Lin et al. Aluminium hydroxide ultrafine powder extracted from fly ash
CN1168785C (en) Process for preparing nano zirconium oxide powder
CN101195495A (en) Process for producing high purity nano-lithium fluoride
CN101823713A (en) Method for preparing mesoporous silicon carbide material at low temperature
CN101698610A (en) Method for preparing highly-pure beta-Sialon ceramic powders
CN111484050A (en) Preparation method of sphere-like α phase nano-alumina
CN103342366A (en) Method for purifying silicon dioxide from industrial rubber thermal residue
CN103708550A (en) Preparation method of zirconium fluoride
CN111039322A (en) Preparation method of high-activity zirconia

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant