CN106799261B - A kind of Al doping ZrO2It is situated between and sees crystal and its preparation method and application - Google Patents
A kind of Al doping ZrO2It is situated between and sees crystal and its preparation method and application Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 45
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 208000011580 syndromic disease Diseases 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
Abstract
The invention discloses a kind of Al to adulterate ZrO2It is situated between and sees crystal and preparation method thereof, belongs to the preparation field of metal oxide functional material.The present invention is dissolved in the water sodium chloride, aluminum nitrate, zirconium oxychloride and urea to form mixed solution in proportion, through 150 DEG C of 24 h of hydro-thermal reaction, the Al is made and adulterates ZrO2It is situated between and sees crystal.Preparation method of the present invention is simple and easy to do, at low cost, and being situated between, it is high to see crystal yield；Obtained Al adulterates ZrO2It is situated between and sees crystal with good monodispersity, in near-spherical or disc-shaped, internal porous, BET specific surface area is up to 160~172m2/ g is a kind of excellent water gas converting catalyst carrier.
Description
Technical field
The invention belongs to the preparation fields of metal oxide functional material, and in particular to a kind of Al doping ZrO2It is situated between and sees crystal
And its preparation method and application.
Background technology
It is situated between and sees crystal（Abbreviation mesomorphic）It is a kind of novel crystalline material, it refers to that nanocrystalline primitive takes according to particular crystal
To nanocrystalline superstructure or ordered aggregation made of orderly accumulation, inside usually there are bulk deposition hole and can show class
The electronic diffraction behavior of monocrystalline.Mesomorphic material has the architectural characteristic of monocrystalline and polycrystalline material simultaneously, it is made industrially to have
Important application value becomes the contenders of monocrystalline and polycrystalline material.Currently, related functionality oxide mesomorphic material
Controllable preparation and performance study are still a research topic for having much challenge.
Zirconium dioxide（ZrO2）It is a kind of highly important functional material, it has surface acidity, alkalinity and oxidation simultaneously
Property, reproducibility, it also has good thermal stability, these performances make ZrO2As a kind of critically important catalyst material.Al
Member is usually carried out modulation ZrO as auxiliary agent2Or the physical and chemical properties of zirconium-containing catalyst.By the ZrO of Al additive modifications2Base is urged
Agent shows excellent catalysis in CO is aoxidized, CO restores the reactions such as NO, preparing cyclohexanone by cyclohexanol dehydrogenation, methanol steam reforming
Performance.The ZrO of Al doping2Being situated between, it is equally possible with important potential using value to see crystal.However, there has been no Al up to now
Adulterate ZrO2It is situated between and sees the open report of crystal and its technology of preparing and application.
Invention content
The purpose of the present invention is to provide a kind of Al to adulterate ZrO2It is situated between and sees crystal and its preparation method and application, preparation side
Method is simple and easy to do, and large-scale production, Al obtained is suitble to adulterate ZrO2The sight crystal product monodispersity that is situated between is good, BET specific surface area
Up to 160~172m2/ g, inside have abundant duct, are a kind of excellent catalyst materials, become be especially suitable for water-gas
Catalyst changeout carrier.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of Al doping ZrO2It is situated between and sees the preparation method of crystal comprising following steps：
（1）Sodium chloride, aluminum nitrate, zirconium oxychloride and urea are dissolved in deionized water, are made mixed after stirring at room temperature
Close solution；
（2）By step（1）Gained mixed solution is transferred in pyroreaction kettle, and controlling reaction temperature is 150 DEG C, when reaction
Between be 24 h；Gained reaction product is centrifuged, washs, dry after obtain Al doping ZrO2It is situated between and sees crystal.
Step（1）The substance withdrawl syndrome of sodium chloride is 0~0.005mol/L in mixed solution；Aluminum nitrate and zirconium oxychloride
The sum of substance withdrawl syndrome be 0.75 mol/L, the amount of the substance of aluminum nitrate accounts for aluminum nitrate and the amount of zirconium oxychloride total material
2%~5%；The substance withdrawl syndrome of urea is 1.5 mol/L.
Gained Al adulterates ZrO2It is situated between and sees crystal as monocline crystalline phase, pattern is near-spherical or disc-shaped, near-spherical a diameter of 30
~100 nm；A diameter of 70~200 nm of disc-shaped, thickness are 30~70 nm；BET specific surface area is 160~172 m2/ g, it is interior
Portion is porous, and most probable pore size is 2 nm.
Gained Al adulterates ZrO2The sight crystal that is situated between can be used as carrier and prepare water gas converting catalyst, and preparation method is：
Under ultrasonic disruption subsidiary conditions, the Al is adulterated into ZrO2The sight crystal that is situated between is scattered in copper nitrate aqueous solution, is stated then up
Lye is added dropwise in solution to pH value of solution=9.0, Water gas shift/WGS catalysis is made in gained precipitation after centrifuge washing, drying, roasting
Agent；Lye used is the aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide or sodium hydroxide.
Generation hydrogen is reacted in homogeneous precipitation under hydrothermal conditions with urea for aluminum nitrate and zirconium oxychloride in preparation process of the present invention
Oxide.Under the action of NaCl mineralizers, hydroxide predecessor is by sloughing hydroxyl（Or dehydration）, atom in situ reset and
It is changed into crystalline state Al doping ZrO2, that is, Al is precipitated and adulterates ZrO2Nanocrystal.Crystal grain is in reaction system selffield
（Nanocrystalline natural dipole moment）Lower realization crystalline orientation aggregation, forms the ZrO of adulterated al2It is situated between and sees crystal superstructure.
The remarkable advantage of the present invention is：
（1）The ZrO of near-spherical and disc-shaped doping Al is prepared by this method for the first time2It is situated between and sees crystal, preparation method is easy
It is easy, it is suitble to large-scale production, gained Al to adulterate ZrO2It is situated between and sees crystal yield height, monodispersity is good, good crystallinity, and BET compares table
Area is up to 160~172m2/ g, product grain internal gutter is abundant, and most probable pore size is 2 nm inside particle.
（2）Al prepared by the present invention adulterates ZrO2Mesomorphic is a kind of excellent catalyst carrier, is prepared using it as carrier
Copper-based catalysts show excellent water gas shift reaction producing hydrogen, catalyzing performance.When CuO contents are 10 wt%, Al doping
ZrO2CO high conversion rate of the CuO Catalyst Supported when reaction temperature is 240 DEG C is up to 94%, hence it is evident that is higher than the ZrO of non-impurity-doped Al2
Mesomorphic CuO Catalyst Supported（When reaction temperature is 240 DEG C, CO conversion ratios are 83%）With conventional polysilicon ZrO2Supported CuO is catalyzed
Agent（When reaction temperature is 240 DEG C, CO conversion ratios are 69%）.
Description of the drawings
Fig. 1 is Al doping ZrO prepared by embodiment 12It is situated between and sees the XRD diagram of crystal.
Fig. 2 is Al doping ZrO prepared by embodiment 12It is situated between and sees the SEM figures of crystal.
Fig. 3 is Al doping ZrO prepared by embodiment 12It is situated between and sees the TEM figures of crystal.
Fig. 4 is Al doping ZrO prepared by embodiment 12It is situated between and sees the selective electron diffraction of crystal（SAED）Figure.
Fig. 5 is Al doping ZrO prepared by embodiment 22It is situated between and sees the SEM figures of crystal.
Fig. 6 is Al doping ZrO prepared by embodiment 32It is situated between and sees the SEM figures of crystal.
Specific implementation mode
Below by embodiment, invention is further explained, but the present invention is not limited in these embodiments.
Embodiment 1
By 0.39 g aluminum nitrates, 16.58 g zirconium oxychlorides and 6.31 g urea are dissolved in 50mL deionized waters, are stirred at room temperature
Mixed solution is made after mixing（The amount of the substance of aluminum nitrate accounts for the 2% of aluminum nitrate and the amount of zirconium oxychloride total material）, by above-mentioned mixing
Liquid is transferred to after being demarcated to 70mL with deionized water in the pyroreaction kettle that volume is 100mL.Reaction kettle is put into air dry oven
Interior, controlling reaction temperature is 150 DEG C, and the reaction time is 24 hours.Products therefrom is after centrifuge washing imurity-removal ion in 60
DEG C obtain within dry 8 hours Al doping ZrO2It is situated between and sees crystal.
Fig. 1 is Al doping ZrO manufactured in the present embodiment2It is situated between and sees the XRD diagram of crystal.As shown in Figure 1, prepared Al doping
ZrO2In monocline crystalline phase.
Fig. 2, Fig. 3 are Al doping ZrO manufactured in the present embodiment respectively2It is situated between and sees the SEM figures and TEM figures of crystal.By Fig. 2 and figure
3 it is found that Al adulterates ZrO2Particle is in near-spherical and is assembled by numerous little crystal grains, a diameter of the 40~100 of near-spherical particle
Nm is covered with nano aperture inside particle.
Fig. 4 is Al doping ZrO manufactured in the present embodiment2It is situated between and sees the selective electron diffraction of crystal（SAED）Figure.As seen from Figure 4
Single Al adulterates ZrO2Class monocrystalline electronic diffraction behavior is presented in particle, i.e., primary intercrystalline lattice matched inside particle,
Show that Al adulterates ZrO2Crystal is seen to be situated between.
N2The experiment of physics adsorption desorption shows that the Al adulterates ZrO2The BET specific surface area of mesomorphic is 160 m2/ g, inside particle
Most probable pore size is 2 nm.
Embodiment 2
By 0.01 g sodium chloride, 0.59 g aluminum nitrates, 16.41 g zirconium oxychlorides and 6.31 g urea are dissolved in 50mL deionizations
In water, mixed solution is made after stirring at room temperature（The amount of the substance of aluminum nitrate accounts for aluminum nitrate and the amount of zirconium oxychloride total material
3%）, it is transferred in the pyroreaction kettle that volume is 100mL after above-mentioned mixed liquor is demarcated with deionized water to 70mL.By reaction kettle
It is put into air dry oven, controlling reaction temperature is 150 DEG C, and the reaction time is 24 hours.Products therefrom is removed through centrifuge washing
Al is obtained within dry 8 hours in 60 DEG C adulterate ZrO after foreign ion2It is situated between and sees crystal.
Fig. 5 is Al doping ZrO manufactured in the present embodiment2It is situated between and sees the SEM figures of crystal.Fig. 5 shows prepared Al doping
ZrO2Particle is similarly near-spherical Jie and sees crystal, a diameter of 30~90 nm.
N2The experiment of physics adsorption desorption shows that the Al adulterates ZrO2The BET specific surface area of mesomorphic is 165 m2/ g, inside particle
Most probable pore size is 2 nm.
Embodiment 3
By 0.02 g sodium chloride, 0.98 g aluminum nitrates, 16.07 g zirconium oxychlorides and 6.31 g urea are dissolved in 50mL deionizations
In water, mixed solution is made after stirring at room temperature（The amount of the substance of aluminum nitrate accounts for aluminum nitrate and the amount of zirconium oxychloride total material
5%）, it is transferred in the pyroreaction kettle that volume is 100mL after above-mentioned mixed liquor is demarcated with deionized water to 70mL.By reaction kettle
It is put into air dry oven, controlling reaction temperature is 150 DEG C, and the reaction time is 24 hours.Products therefrom is removed through centrifuge washing
Al is obtained within dry 8 hours in 60 DEG C adulterate ZrO after foreign ion2It is situated between and sees crystal.
Fig. 6 is Al doping ZrO manufactured in the present embodiment2It is situated between and sees the SEM figures of crystal.Fig. 6 shows prepared Al doping
ZrO2Particle is that disc-shaped Jie sees crystal, a diameter of 70~200 nm, and thickness is 30~70 nm.
N2The experiment of physics adsorption desorption shows that the Al adulterates ZrO2The BET specific surface area of mesomorphic is 172 m2/ g, inside particle
Most probable pore size is 2 nm.
Application Example 1
ZrO is adulterated with Al made from embodiment 12It is situated between and sees crystal as carrier loaded CuO preparation Cu base mesomorphic catalyst, method
It is as follows：The Al after 250 DEG C of roastings of 3g is adulterated into ZrO under the auxiliary of ultrasonication2The sight crystal that is situated between is scattered in 200mL
In the Gerhardite aqueous solution of 0.021mol/L, the potassium hydroxide aqueous solution that 0.5mol/L is added dropwise in solution is stated then up
PH=9.0 to terminal.It is 8 hours dry in 120 DEG C after the washed imurity-removal ion of products therefrom, it is small then at 400 DEG C of roastings 4
When be made Al adulterate ZrO2Mesomorphic CuO Catalyst Supported.
Application Example 2
ZrO is adulterated with Al made from embodiment 22It is situated between and sees crystal as carrier loaded CuO preparation Cu base mesomorphic catalyst, system
Preparation Method and condition are identical as Application Example 1.
Application Example 3
ZrO is adulterated with Al made from embodiment 32It is situated between and sees crystal as carrier loaded CuO preparation Cu base mesomorphic catalyst, system
Preparation Method and condition are identical as Application Example 1.
Comparison study example 1：ZrO2Polycrystalline CuO Catalyst Supported
7.85g zirconium oxychlorides are dissolved in 200mL deionized waters, reaction bottom liquid is made, by the hydroxide of 0.5mol/L
Above-mentioned reaction bottom liquid pH=9.0 to terminal are added in aqueous solutions of potassium.In 60 DEG C of dryings after the washed imurity-removal ion of products therefrom
8 hours, then at 250 DEG C of roastings, 4 hours obtained ZrO2Polycrystalline.
By 3g ZrO under the auxiliary of ultrasonic disruption2Polycrystalline is scattered in the Gerhardite of 200mL 0.021mol/L
In aqueous solution, potassium hydroxide aqueous solution pH=9.0 to terminal that 0.5mol/L is added dropwise in solution are stated then up.Products therefrom
It is 8 hours dry in 120 DEG C after washed imurity-removal ion, then at 400 DEG C of roastings, 4 hours obtained ZrO2Polycrystalline Supported CuO is urged
Agent.
Comparison study example 2：ZrO2Mesomorphic CuO Catalyst Supported
16.92g zirconium oxychlorides and 6.31 g urea are dissolved in 50mL deionized waters, it is molten that mixing is made after stirring at room temperature
Liquid.It is transferred in the pyroreaction kettle that volume is 100mL after above-mentioned mixed liquor is demarcated with deionized water to 70mL.Reaction kettle is put
Enter in air dry oven, controlling reaction temperature is 150 DEG C, and the reaction time is 24 hours.Products therefrom removes miscellaneous through centrifuge washing
After matter ion ZrO is obtained in 60 DEG C within dry 8 hours2It is situated between and sees crystal.
By the ZrO for not mixing Al after 250 DEG C of roastings of 3g under the auxiliary of ultrasonic disruption2The sight crystal that is situated between is scattered in 200mL
In the Gerhardite aqueous solution of 0.021mol/L, the potassium hydroxide aqueous solution that 0.5mol/L is added dropwise in solution is stated then up
PH=9.0 to terminal.It is 8 hours dry in 120 DEG C after the washed imurity-removal ion of products therefrom, it is small then at 400 DEG C of roastings 4
When be made ZrO2Mesomorphic CuO Catalyst Supported.
Activity rating
The catalytic activity of catalyst is tested using water gas shift reaction as probe reaction, activity rating is atmospheric fixed bed anti-
It answers and is carried out on device, evaluation condition：Unstripped gas is simulation methane reforming gas, and volumn concentration group becomes 15% CO, 55% H2,
7% CO2, 23% N2。
Catalytic activity is indicated with CO conversion ratios, to the activity of catalyst obtained by Application Example 1-3 and Comparison study example 1-2
It is evaluated, result such as table 1.
The Activity evaluation of catalyst obtained by 1 Application Example 1-3 of table and Comparison study example 1-2
It can be seen that and ZrO2Mesomorphic CuO Catalyst Supported and tradition ZrO2Polycrystalline CuO Catalyst Supported is compared, with this hair
Bright Al adulterates ZrO2The sight crystal that is situated between is that CuO Catalyst Supported prepared by carrier lives to water gas shift reaction with higher catalysis
Property, that is, illustrate the Al doping ZrO prepared by the present invention2The sight crystal that is situated between is a kind of excellent catalyst carrier.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (1)
1. a kind of Al adulterates ZrO2It is situated between and sees the preparation method of crystal, which is characterized in that includes the following steps：
（1）Sodium chloride, aluminum nitrate, zirconium oxychloride and urea are dissolved in deionized water, it is molten that mixing is made after stirring at room temperature
Liquid；
（2）By step（1）Gained mixed solution is transferred in pyroreaction kettle, and controlling reaction temperature is 150 DEG C, and the reaction time is
24 h；Gained reaction product is centrifuged, washs, dry after obtain the Al doping ZrO2It is situated between and sees crystal；
Step（1）The substance withdrawl syndrome of sodium chloride is 0~0.005mol/L in mixed solution；The object of aluminum nitrate and zirconium oxychloride
The sum of amount concentration of matter is 0.75 mol/L, the amount of the substance of aluminum nitrate account for aluminum nitrate and the amount of zirconium oxychloride total material 2%~
5%；The substance withdrawl syndrome of urea is 1.5 mol/L；
Gained Al adulterates ZrO2It is situated between and sees crystal, pattern is near-spherical or disc-shaped；A diameter of 30~100 nm of near-spherical；Disc-shaped
A diameter of 70~200 nm, thickness are 30~70 nm；BET specific surface area is 160~172 m2/ g, internal porous, most probable hole
Diameter is 2 nm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599779A (en) * | 2013-11-13 | 2014-02-26 | 福州大学 | CuO/ZrO2 water-gas shift catalyst and preparation method thereof |
| CN104353455A (en) * | 2014-11-05 | 2015-02-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Au-loaded different-crystalline-phase ZrO2 catalyst as well as preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009114008A (en) * | 2007-11-02 | 2009-05-28 | Sakai Chem Ind Co Ltd | Zirconium oxide fine powder, method for producing the same, and resin composition comprising the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599779A (en) * | 2013-11-13 | 2014-02-26 | 福州大学 | CuO/ZrO2 water-gas shift catalyst and preparation method thereof |
| CN104353455A (en) * | 2014-11-05 | 2015-02-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Au-loaded different-crystalline-phase ZrO2 catalyst as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| CuO/ZrO2水煤气变换催化剂：制备及构效关系研究;张燕杰;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20161215(第12期);正文第100页第1-3段、第101页第1段、第106页第1-2段、第110页第3段 * |
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