CN103523830B - High-specific-surface area pure-monoclinic-phase zirconia preparation method - Google Patents
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 33
- 239000003929 acidic solution Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- -1 zirconium ions Chemical class 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 61
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 239000000693 micelle Substances 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 25
- 239000002002 slurry Substances 0.000 description 15
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 230000003252 repetitive effect Effects 0.000 description 6
- 238000005201 scrubbing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Abstract
The invention discloses a high-specific-surface area pure-monoclinic-phase zirconia preparation method. The method sequentially comprises the steps that: (1) an acidic solution comprising zirconium ions and with a pH value lower than 5 is formed; (2) the solution is heated for 3-120h under a temperature of 80-300 DEG C, such that the solution forms monoclinic-phase zirconia colloidal particles or tiny solid particles comprising crystal water, wherein the zirconium concentration in the acidic solution is maintained unchanged. (3) the pH value of the solution is regulated to 5-11, such that the monoclinic-phase zirconia colloidal particles or tiny solid particles are deposited; (4) the solution is filtered; an obtained filter cake is washed until no impurity ion is left; and drying is carried out; and (5) the washed and dried filter cake is roasted, such that crystal water is removed, and high-specific-surface area pure-monoclinic-phase zirconia is obtained. The prepared pure-monoclinic-phase zirconia can be used as a carrier for various catalysts.
Description
Technical field
The present invention relates to a kind of preparation method of pure monoclinic phase zirconium dioxide of high-specific surface area.
Background technology
Zirconium dioxide is a kind of important key industry raw material, and it has in a lot of field applies extremely widely, such as chemical field, fine materials field and catalyst field,
Zirconium dioxide have unformed, monocline, four directions and cube etc. multiple phase, the physics and chemistry of the zirconium dioxide of different phase is distinct, and in various synthetic gas catalyzed reaction, it often shows higher catalytic reaction activity and selectivity of product.Thus, the application of the pure monoclinic phase zirconium dioxide of high-specific surface area brings qualitative leap by giving the catalyst efficiency of many catalyzed reactions.
But the pure monoclinic phase zirconium dioxide preparing high-specific surface area is very difficult, so far, the real simple and preparation method of the pure monoclinic phase zirconium dioxide of the high-specific surface area of practicality is there are no report.
Conventional zirconium dioxide preparation method utilizes neutralization reaction to produce the sedimentary precipitator method of zirconium dioxide presoma, but the zirconium dioxide that this precipitator method obtain is often the mixture of monoclinic phase and Tetragonal or Emission in Cubic, is not the zirconium dioxide of pure monoclinic phase.
Now, industrial, pure monoclinic phase zirconium dioxide mainly obtains by sintering process, and its sintering temperature is usually above 1000 DEG C.High temperature sintering causes the specific surface area of obtained pure monoclinic phase zirconium dioxide greatly to reduce, and therefore, the specific surface area of industrial conventional monoclinic phase zirconium dioxide is mostly lower than 50m
2/ g, most low 25m
2/ g.
CN102627323A discloses a kind of monoclinic phase zirconia nanocrystals raw powder's production technology, the method mixes with zirconium nitrate solution and citric acid by adding lithium ion, after forming xerogel, roasting under 600-1000 DEG C of high temperature again, obtain monoclinic phase zirconia nanocrystals powder, owing to introducing lithium ion in preparation process, the monoclinic phase Zirconium dioxide powder finally obtained not is pure, and this impure monoclinic phase Zirconium dioxide powder can be applicable to prepare the fields such as structural ceramics.But by the restriction such as specific surface and foreign matter content, it is not suitable for contrast table area and the higher catalyst field of purity requirement.
The present invention has aimed to provide a kind of preparation method of pure monoclinic phase zirconium dioxide of high-specific surface area, and this preparation method has that technical process is simple, operation is easy to control, product purity is high, the plurality of advantages such as specific surface area is large.The pure monoclinic phase zirconium dioxide of obtained high-specific surface area is especially suitable for use as support of the catalyst.
Summary of the invention
According to a first aspect of the present invention, provide a kind of preparation method of pure monoclinic phase zirconium dioxide of high-specific surface area, described method comprises the following steps successively:
(1) acidic solution containing zirconium ion that pH value is less than 5 is formed; (2) at 80-300 DEG C of temperature and the above-mentioned acidic solution 3-120 hour of 0.1-3MPa heating under pressure, thus, make the formation of above-mentioned acidic solution contain monoclinic phase zirconium dioxide micelle or the fine solid particle of crystal water, keep the zirconium concentration in above-mentioned acidic solution constant therebetween; (3) regulate the pH value of above-mentioned acidic solution to 5-11, thus, deposit those monoclinic phase zirconium dioxide micelle or fine solid particle; (4) above-mentioned solution is filtered, wash the filter cake obtained, until inclusion-free ion, subsequently, carry out drying; (5) roasting is carried out to washing and dried filter cake, remove crystal water wherein, thus, obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
Usually, in above-mentioned preparation method, but the described zirconium salt solution of acidic solution solubility, the zirconates of solubility and the mixing solutions of acid containing zirconium ion or the mixing solutions of zirconium hydroxide and acid; But one or more in the nitrate of described zirconates zirconium, carbonate, villaumite, oxalate, formate, acetate or ammonium salt such as, are zirconium carbonate, zirconium nitrate, Zircosol ZN, zirconium chloride and/or zirconyl chloride.
Preferably, in above-mentioned steps (1), the pH value of described acidic solution is less than 1 further; In above-mentioned steps (2), by refluxing or supplementing solvent to described acidic solution, to keep the zirconium concentration in above-mentioned acidic solution constant; In above-mentioned steps (3), water-soluble flocculant is used to regulate the pH value of above-mentioned solution, and deposit those monoclinic phase zirconium dioxide micelle or fine solid particle; In above-mentioned steps (4), the repeatedly filter cake that obtains of repeated washing, with imurity-removal, and at 100-140 DEG C dry described filter cake 4-24 hour; In above-mentioned steps (5), at the 400-700 DEG C of above-mentioned washing of roasting temperature and dried filter cake 1-12 hour.
In above-mentioned steps (3), described water-soluble flocculant can be basic solution, such as, be ammoniacal liquor; The pure monoclinic phase zirconium dioxide of described high-specific surface area can have and is greater than 50m
2/ g, even 100m
2the specific surface area of/g.The pure monoclinic phase zirconium dioxide of this high-specific surface area can be used as support of the catalyst.
According to a second aspect of the present invention, provide a kind of loaded catalyst, the carrier of described catalyzer is the pure monoclinic phase zirconium dioxide of the high-specific surface area prepared by aforesaid method.
Accompanying drawing explanation
Fig. 1 is the pure monoclinic phase zirconium dioxide of the high-specific surface area prepared by the inventive method and the contrast figure comprising the X-ray diffracting spectrum of the zirconium dioxide of monoclinic phase and Tetragonal that prepared by conventional precipitation method.
Embodiment
By being further explained in detail the present invention below with reference to the description of embodiment and accompanying drawing, but below describe only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, and do not mean that any type of restriction is carried out to the present invention.
The present inventor finds through lot of experiments: at acidic solution, if the zirconium ion that such as pH value is less than in the solution of 5 stands long-time heating, such as be heated 3-120 hour at 80-300 DEG C, water-fast monoclinic phase zirconium dioxide colloidal particle containing crystal water or very trickle solids can be formed in an acidic solution, by adjusting the pH value of acidic solution, the zirconium dioxide colloidal particle of these pure monoclinic phases or fine particle can be made to deposit, thus, realization is separated with solution, because these particle purity are very high, particle diameter is also very little, they manufacture the best raw material of the pure monoclinic phase zirconium dioxide of high-specific surface area.
Said process can carry out under normal pressure or high-pressure situations.The particle obtained through simple filter and washing, remove water-soluble impurity after, then through the roasting of suitable temp, just can obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
Aforesaid method and traditional precipitator method or coprecipitation method completely different, the precipitator method or coprecipitation method utilize neutralization reaction, by adding the pH value of precipitation agent adjustment solution, the zirconium particle in solution is made to form the throw out containing zirconium, i.e. zirconium hydroxide, again by the zirconium hydroxide of roasting as zirconium white presoma, finally obtain zirconium dioxide, in the process, first, need that the pH value of solution is transferred to more than 7 and just likely produce throw out, secondly, because zirconium hydroxide is when decomposes is zirconium dioxide, in different temperature ranges, different crystalline phases can be formed, so, the zirconium dioxide that this method obtains will be the mixture of monoclinic phase and Tetragonal or Emission in Cubic, it is not the zirconium dioxide of pure monoclinic phase.
, further illustrate the present invention by concrete one exemplary embodiment below, but these embodiments do not form any restriction to scope.
Embodiment
Embodiment 1
By 32.22 grams of ZrOCl
28H
2o is dissolved in 100 grams of deionized waters, after forming acidic solution, then is inserted in there-necked flask.
There-necked flask is put into 120 DEG C of oil bath pans to heat, stir simultaneously, and reflux to the water in solution, after 24 hours, solution becomes slurries, from oil bath pan, take out slurries, and regulates its pH value to 5 with ammoniacal liquor.
Filter the slurries obtained, with deionized water repetitive scrubbing filter cake, until silver nitrate solution can't detect chlorion, then dry 12 hours in 120 DEG C of loft drier, obtain dry powder.
The powder of above-mentioned drying to be inserted in 500 DEG C of retort furnaces roasting 2 hours, obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
Embodiment 2
By 16 grams of Zr (OH)
4put into there-necked flask, then add salpeter solution and 3 grams of polyvinyl alcohol (molecular weight is 1000-2000) that 100 grams of concentration are 20 % by weight, form acidic solution.
There-necked flask is put into 110 DEG C of water-baths to heat, stir simultaneously, and reflux to the water in solution, after 48 hours, solution becomes slurries, from water-bath, take out slurries, and regulates its pH value to 7 with ammoniacal liquor.
Filter the slurries obtained, with deionized water repetitive scrubbing filter cake, then dry 6 hours in 120 DEG C of loft drier, obtain dry powder.
The powder of above-mentioned drying to be inserted in 500 DEG C of retort furnaces roasting 1 hour, obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
Embodiment 3
By 26.73 grams of ZrO (NO
3)
22H
2o is dissolved in 100 grams of deionized waters, after forming acidic solution, then is inserted in there-necked flask.
There-necked flask is put into 80 DEG C of oil bath pans to heat, stir simultaneously, and reflux to the water in solution, after 24 hours, solution becomes slurries, from oil bath pan, take out slurries, and regulates its pH value to 10 with ammoniacal liquor.
Filter the slurries obtained, with deionized water repetitive scrubbing filter cake, then dry 12 hours in 120 DEG C of loft drier, obtain dry powder.
The powder of above-mentioned drying to be inserted in 500 DEG C of retort furnaces roasting 4 hours, obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
Embodiment 4
By 21.12 grams of Zr (CO
3)
2insert in autoclave, then add the sulphuric acid soln that 100 grams of concentration are 30 % by weight, form acidic solution.
Autoclave is heated to 200 DEG C, and stirs acidic solution wherein, keep constant temperature after 12 hours, stop heating, solution becomes slurries, from autoclave, take out slurries, and regulates its pH value to 8 with ammoniacal liquor.
Filter the slurries obtained, with deionized water repetitive scrubbing filter cake, then in 120 DEG C of loft drier, dry filter cake 6 hours, obtain dry powder.
The powder of above-mentioned drying to be inserted in 400 DEG C of retort furnaces roasting 4 hours, obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
Embodiment 5
By 30 grams of Zr (NO
3)
4be dissolved in 100 grams of deionized waters, then add 3 grams of polyvinyl alcohol (molecular weight is 1000-2000), form acidic solution.
Acidic solution is put into autoclave, then autoclave is heated to 300 DEG C, and acidic solution is wherein stirred, keep constant temperature after 6 hours, stop heating, solution becomes slurries, from autoclave, take out slurries, and regulate its pH value to 8 with ammoniacal liquor.
Filter the slurries obtained, with deionized water repetitive scrubbing filter cake, then in 120 DEG C of loft drier, dry filter cake 6 hours, obtain dry powder.
The powder of above-mentioned drying to be inserted in 600 DEG C of retort furnaces roasting 8 hours, obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
Comparative example 1: the precipitator method prepare zirconium dioxide
By 32.22 grams of ZrOCl
28H
2o is dissolved in 100 grams of deionized waters, after forming acidic solution, then inserts in there-necked flask.
There-necked flask is put into 60 DEG C of oil bath pans to heat, stir simultaneously, drip ammoniacal liquor lentamente in oxytropism solution, make solution carry out precipitin reaction, when solution ph is increased to 8, stop dripping ammoniacal liquor, precipitin reaction terminates.
Filter and produce sedimentary solution, with deionized water repetitive scrubbing filter cake, until silver nitrate solution can't detect chlorion, then dry 12 hours in 120 DEG C of loft drier, obtain dry powder.
The powder of above-mentioned drying to be inserted in 600 DEG C of retort furnaces roasting 4 hours, obtain the zirconium dioxide of monoclinic phase and Tetragonal mixing.
Test case
Test case 1 measures crystalline phase and specific surface area
Measured the crystalline phase of Zirconium dioxide powder in embodiment 1-5 and comparative example 1 by X-ray diffracting spectrum, then measure the specific surface area of Zirconium dioxide powder in embodiment 1-5 and comparative example 1 by BET method.
As can be seen from Figure 1: the characteristic peak of monoclinic phase and Tetragonal has appearred in the Zirconium dioxide powder X-ray diffracting spectrum in comparative example 1, illustrate that powder is the mixture of monoclinic phase zirconium dioxide and tetragonal zirconium dioxide; And monoclinic phase characteristic peak has only appearred in the Zirconium dioxide powder X-ray diffracting spectrum in embodiment 1-5, illustrate that powder is pure monoclinic phase zirconium dioxide.
The table with test results of the Zirconium dioxide powder crystalline phase in embodiment 1-5 and comparative example 1 and specific surface area is shown in the following Table 1.
Table 1
Table 1 absolutely proves: the inventive method has prepared the pure monoclinic phase Zirconium dioxide powder of high-specific surface area, and this powder is especially suitable for use as the carrier of catalyzer.And the precipitator method in comparative example 1 only can prepare the mixture of monoclinic phase zirconium dioxide and tetragonal zirconium dioxide.
The term that this specification sheets is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its integral part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary; those skilled in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (7)
1. a preparation method for the pure monoclinic phase zirconium dioxide of high-specific surface area, described method comprises the following steps successively:
(1) acidic solution containing zirconium ion that pH value is less than 5 is formed;
(2) at 80-300 DEG C of temperature, above-mentioned acidic solution 3-120 hour is heated, thus, make above-mentioned acidic solution form the monoclinic phase zirconium dioxide micelle containing crystal water, keep the zirconium concentration in above-mentioned acidic solution constant therebetween;
(3) regulate the pH value of above-mentioned acidic solution to 5-11, thus, deposit those monoclinic phase zirconium dioxide micelle;
(4) above-mentioned solution is filtered, wash the filter cake obtained, until inclusion-free ion, subsequently, carry out drying;
(5) at 400-700 DEG C of temperature, roasting is carried out to washing and dried filter cake, remove crystal water wherein, thus, obtain the pure monoclinic phase zirconium dioxide of high-specific surface area.
2. preparation method according to claim 1, wherein, the described acidic solution containing zirconium ion is the zirconium salt solution of solubility, the zirconates of solubility and the mixing solutions of acid or the mixing solutions of zirconium hydroxide and acid.
3. preparation method according to claim 2.Wherein, described zirconates is one or more in the nitrate of zirconium, carbonate, villaumite, oxalate, formate, acetate or ammonium salt.
4. preparation method according to claim 3, wherein, described zirconates is zirconium carbonate, zirconium nitrate, Zircosol ZN, zirconium chloride and/or zirconyl chloride further.
5. preparation method according to claim 1, wherein, in above-mentioned steps (1), the pH value of described acidic solution is less than 1 further; In above-mentioned steps (2), by refluxing or supplementing solvent to described acidic solution, to keep the zirconium concentration in above-mentioned acidic solution constant; In above-mentioned steps (3), water-soluble flocculant is used to regulate the pH value of above-mentioned solution, and deposit those monoclinic phase zirconium dioxide micelle; In above-mentioned steps (4), the repeatedly filter cake that obtains of repeated washing, with imurity-removal, and at 100-140 DEG C dry described filter cake 4-24 hour; In above-mentioned steps (5), at the 400-700 DEG C of above-mentioned washing of roasting temperature and dried filter cake 1-12 hour.
6. preparation method according to claim 5, wherein, described water-soluble flocculant is ammoniacal liquor.
7. preparation method according to claim 1, wherein, the pure monoclinic phase zirconium dioxide of described high-specific surface area has and is greater than 50m
2the specific surface area of/g.
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| CN107915255B (en) * | 2016-10-10 | 2020-10-16 | 中国石油化工股份有限公司 | Preparation method of nano zirconia and nano zirconia prepared by preparation method |
| CN109382094B (en) * | 2017-08-04 | 2021-11-09 | 国家能源投资集团有限责任公司 | Sulfur-tolerant methanation catalyst, preparation method thereof and methanation method |
| CN111573728B (en) * | 2020-05-15 | 2022-04-19 | 浙江金琨锆业有限公司 | Pure monoclinic phase nano-grade zirconium dioxide powder with ultrahigh specific surface area and preparation method thereof |
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| CN102093051A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | Zirconia nano ceramic material |
| CN101830506A (en) * | 2010-05-18 | 2010-09-15 | 潍坊天福化学科技有限公司 | Preparation method of high-purity nano zirconium dioxide |
| CN103288131B (en) * | 2012-12-27 | 2016-02-03 | 西安迈克森新材料有限公司 | The highly active yttrium stable zirconium oxide raw powder's production technology of a kind of low monoclinic phase |
| CN103288132B (en) * | 2013-06-07 | 2014-08-20 | 中国矿业大学 | Preparation method of graded monoclinic phase ZrO2 nanosheet |
-
2013
- 2013-10-29 CN CN201310521606.5A patent/CN103523830B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058277A (en) * | 2013-02-05 | 2013-04-24 | 山东国瓷功能材料股份有限公司 | Supercritical hydrothermal synthesis method of nanometer zirconium oxide powder |
Non-Patent Citations (1)
| Title |
|---|
| "二氧化锆负载催化剂的应用";杨淑梅等;《工业催化》;20031031;第11卷(第10期);第39页摘要部分 * |
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