CN106799261A - 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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- CN106799261A CN106799261A CN201710055913.7A CN201710055913A CN106799261A CN 106799261 A CN106799261 A CN 106799261A CN 201710055913 A CN201710055913 A CN 201710055913A CN 106799261 A CN106799261 A CN 106799261A
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- 239000013078 crystal Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000000243 solution 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
- 239000011148 porous material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 208000011580 syndromic disease Diseases 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 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
- 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
- 238000002336 sorption--desorption measurement Methods 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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction 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
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 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
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 238000011156 evaluation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Al doping ZrO2It is situated between and sees crystal and preparation method thereof, belongs to the preparation field of metal oxide functional material.Sodium chloride, aluminum nitrate, zirconium oxychloride and urea are dissolved in the water to form mixed solution in proportion by the present invention, through 150 DEG C of h of hydro-thermal reaction 24, the Al doping ZrO are obtained2It is situated between and sees crystal.Preparation method is simple of the present invention is easy, low cost, and being situated between, it is high to see crystal yield；Obtained Al doping ZrO2The sight crystal that is situated between has good monodispersity, and 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 field 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 new crystalline material, it refers to that nanocrystalline primitive takes according to particular crystal
To the nanocrystalline superstructure or ordered aggregation of orderly accumulation, generally there is bulk deposition hole and can show class in its inside
The electronic diffraction behavior of monocrystalline.Mesomorphic material has the architectural characteristic of monocrystalline and polycrystalline material simultaneously, it is industrially had
Important application value, the contenders as monocrystalline and polycrystalline material.At present, about feature 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, alkalescence and oxidation simultaneously
Property, reproducibility, it also has good heat endurance, and these performances make ZrO2As a kind of critically important catalyst material.Al
Unit is usually carried out modulation ZrO as auxiliary agent2Or the process based prediction model of zirconium-containing catalyst.By the ZrO of Al additive modifications2Base is urged
Agent shows excellent catalysis in the reactions such as CO oxidations, CO reduction 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, not yet there is Al up to now
Doping ZrO2It is situated between and sees the open report of crystal and its technology of preparing and application.
The content of the invention
It is an object of the invention to provide a kind of Al doping ZrO2It is situated between and sees crystal and its preparation method and application, its preparation side
Method is simple and easy to do, is adapted to large-scale production, obtained Al doping ZrO2The sight crystal product monodispersity that is situated between is good, BET specific surface area
Up to 160~172m2/ g, inside has abundant duct, is a kind of excellent catalyst material, is especially suitable for use as water-gas change
Catalyst changeout carrier.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of Al doping ZrO2It is situated between and sees the preparation method of crystal, it is comprised the following steps：
（1）Sodium chloride, aluminum nitrate, zirconium oxychloride and urea are dissolved in deionized water, it is molten that mixing is obtained 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 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
Substance withdrawl syndrome sum be 0.75 mol/L, the amount of the material of aluminum nitrate accounts for aluminum nitrate with the amount of zirconium oxychloride total material
2%~5%；The substance withdrawl syndrome of urea is 1.5 mol/L.
Gained Al doping ZrO2It is situated between and sees crystal for 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 is 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 doping ZrO2The sight crystal that is situated between can be used as carrier and prepare water gas converting catalyst, and its preparation method is：
Under ultrasonic disruption subsidiary conditions, by Al doping ZrO2The sight crystal that is situated between is scattered in copper nitrate aqueous solution, is stated then up
Alkali lye to pH value of solution=9.0 is added dropwise in solution, gained is precipitated and be obtained after centrifuge washing, drying, roasting Water gas shift/WGS catalysis
Agent；Alkali lye used is the aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide or NaOH.
Homogeneous precipitation reaction generates hydrogen under hydrothermal conditions with urea for aluminum nitrate and zirconium oxychloride in preparation process of the present invention
Oxide.In the presence of NaCl mineralizers, hydroxide predecessor is by sloughing hydroxyl（Or dehydration）, the in situ rearrangement of atom and
It is changed into crystalline state Al doping ZrO2, that is, separate out Al doping ZrO2Nanocrystal.Crystal grain is in reaction system selffield
（Nanocrystalline natural dipole moment）Under realize crystalline orientation assemble, formed adulterated al ZrO2It is situated between and sees crystal superstructure.
Remarkable advantage of the invention is：
（1）The ZrO of near-spherical and disc-shaped doping Al is prepared by this method first2It is situated between and sees crystal, its preparation method is simple and easy to do,
It is adapted to large-scale production, gained Al doping ZrO2Being situated between, sight crystal yield is high, and monodispersity is good, and good crystallinity, BET specific surface area is high
Up to 160~172m2/ g, product grain internal gutter enriches, and particle inside most probable pore size is 2 nm.
（2）Al doping ZrO prepared by the present invention2Mesomorphic is a kind of excellent catalyst carrier, is prepared by carrier with it
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 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%）.
Brief description of the drawings
Fig. 1 is Al doping ZrO prepared by embodiment 12It is situated between and sees the XRD 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 SEAD 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 embodiment
The present invention is further described below by embodiment, 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, after stirring at room temperature
Mixed solution is obtained（The amount of the material of aluminum nitrate accounts for the 2% of aluminum nitrate and the amount of zirconium oxychloride total material）, above-mentioned mixed liquor is used
Deionized water is demarcated to after 70mL and is transferred in the pyroreaction kettle that volume is 100mL.Reactor is put into air dry oven, is controlled
Reaction temperature processed is 150 DEG C, and the reaction time is 24 hours.Products therefrom is through centrifuge washing imurity-removal ion after 60 DEG C of dryings
Obtain within 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 of crystal.As shown in Figure 1, prepared Al doping
ZrO2In monocline crystalline phase.
Fig. 2, Fig. 3 are respectively Al doping ZrO manufactured in the present embodiment2It is situated between and sees the SEM figures and TEM figures of crystal.By Fig. 2 and Tu
3 understand, Al doping ZrO2Particle is formed in near-spherical and by the aggregation of numerous little crystal grains, and 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 SEAD of crystal（SAED）Figure.As seen from Figure 4
Single Al doping ZrO2Particle is presented class monocrystalline electronic diffraction behavior, i.e., once intercrystalline lattice matched inside particle,
Show Al doping ZrO2Crystal is seen to be situated between.
N2- physics adsorption desorption is tested and shown, Al doping ZrO2The BET specific surface area of mesomorphic is 160 m2/ g, inside particle
Most probable pore size is 2 nm.
Embodiment 2
0.01 g sodium chloride, 0.59 g aluminum nitrates, 16.41 g zirconium oxychlorides and 6.31 g urea are dissolved in 50mL deionized waters
In, mixed solution is obtained after stirring at room temperature（The amount of the material of aluminum nitrate accounts for aluminum nitrate with the amount of zirconium oxychloride total material
3%）, above-mentioned mixed liquor deionized water is demarcated to after 70mL and is transferred in the pyroreaction kettle that volume is 100mL.By reactor
It is put into air dry oven, controlling reaction temperature is 150 DEG C, the reaction time is 24 hours.Products therefrom is removed through centrifuge washing
Foreign ion obtains Al doping ZrO for 8 hours after 60 DEG C of dryings2It 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 that prepared Al adulterates
ZrO2Particle is similarly near-spherical Jie and sees crystal, its a diameter of 30~90 nm.
N2- physics adsorption desorption is tested and shown, Al doping ZrO2The BET specific surface area of mesomorphic is 165 m2/ g, inside particle
Most probable pore size is 2 nm.
Embodiment 3
0.02 g sodium chloride, 0.98 g aluminum nitrates, 16.07 g zirconium oxychlorides and 6.31 g urea are dissolved in 50mL deionized waters
In, mixed solution is obtained after stirring at room temperature（The amount of the material of aluminum nitrate accounts for aluminum nitrate with the amount of zirconium oxychloride total material
5%）, above-mentioned mixed liquor deionized water is demarcated to after 70mL and is transferred in the pyroreaction kettle that volume is 100mL.By reactor
It is put into air dry oven, controlling reaction temperature is 150 DEG C, the reaction time is 24 hours.Products therefrom is removed through centrifuge washing
Foreign ion obtains Al doping ZrO for 8 hours after 60 DEG C of dryings2It 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 that prepared Al adulterates
ZrO2Particle is that disc-shaped Jie sees crystal, its a diameter of 70~200 nm, and thickness is 30~70 nm.
N2- physics adsorption desorption is tested and shown, Al doping ZrO2The BET specific surface area of mesomorphic is 172 m2/ g, inside particle
Most probable pore size is 2 nm.
Application Example 1
With Al doping ZrO obtained in embodiment 12It is situated between and sees crystal for carrier loaded CuO prepares Cu base mesomorphic catalyst, method is such as
Under：By the Al doping ZrO after 250 DEG C of roastings of 3g 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 of dropwise addition 0.5mol/L in solution is stated then up
PH=9.0 to terminal.The scrubbed imurity-removal ion of products therefrom is small then at 400 DEG C of roastings 4 after 120 DEG C of dryings 8 hours
When be obtained Al doping ZrO2Mesomorphic CuO Catalyst Supported.
Application Example 2
With Al doping ZrO obtained in embodiment 22It is situated between and sees crystal for carrier loaded CuO prepares Cu base mesomorphic catalyst, its preparation side
Method and condition are identical with Application Example 1.
Application Example 3
With Al doping ZrO obtained in embodiment 32It is situated between and sees crystal for carrier loaded CuO prepares Cu base mesomorphic catalyst, its preparation side
Method and condition are identical with Application Example 1.
Comparison study example 1：ZrO2Polycrystalline CuO Catalyst Supported
7.85g zirconium oxychlorides are dissolved in reaction bottom liquid is obtained in 200mL deionized waters, by the potassium hydroxide water of 0.5mol/L
Solution adds above-mentioned reaction bottom liquid pH=9.0 to terminal.The scrubbed imurity-removal ion of products therefrom is small after 60 DEG C of dryings 8
When, then at 250 DEG C of roastings, 4 hours prepared ZrO2Polycrystalline.
By 3g ZrO under the auxiliary of ultrasonic disruption2Polycrystalline is scattered in the Gerhardite of 200mL 0.021mol/L
In the aqueous solution, state the potassium hydroxide aqueous solution of 0.5mol/L pH=9.0 to terminal are added dropwise in solution then up.Products therefrom
Scrubbed imurity-removal ion after 120 DEG C of dryings 8 hours, then at 400 DEG C of roastings, 4 hours prepared 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, mixed solution is obtained after stirring at room temperature.
Above-mentioned mixed liquor deionized water is demarcated to after 70mL and is transferred in the pyroreaction kettle that volume is 100mL.Reactor is put into
In air dry oven, controlling reaction temperature is 150 DEG C, and the reaction time is 24 hours.Products therefrom is through centrifuge washing imurity-removal
Ion obtains ZrO in 8 hours after 60 DEG C of dryings2It 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 of dropwise addition 0.5mol/L in solution is stated then up
PH=9.0 to terminal.The scrubbed imurity-removal ion of products therefrom is small then at 400 DEG C of roastings 4 after 120 DEG C of dryings 8 hours
When be obtained ZrO2Mesomorphic CuO Catalyst Supported.
Activity rating
The catalysis activity of catalyst is tested as probe reaction with water gas shift reaction, activity rating is in atmospheric fixed bed reactor
On carry out, appreciation condition：Unstripped gas is simulation methane reforming gas, and its volumn concentration composition is 15% CO, 55% H2, 7%
CO2, 23% N2。
Catalysis activity is represented with CO conversion ratios, to Application Example 1-3 and the activity of Comparison study example 1-2 gained catalyst
Evaluated, its result such as table 1.
The Activity evaluation of the Application Example 1-3 of table 1 and Comparison study example 1-2 gained catalyst
As can be seen here, with ZrO2Mesomorphic CuO Catalyst Supported and tradition ZrO2Polycrystalline CuO Catalyst Supported is compared, with the present invention
Al doping ZrO2It is situated between and sees crystal for CuO Catalyst Supported prepared by carrier there is catalysis higher to live water gas shift reaction
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 only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (5)
1. a kind of Al doping ZrO2It is situated between and sees the preparation method of crystal, it is characterised in that：Comprise the following steps：
（1）Sodium chloride, aluminum nitrate, zirconium oxychloride and urea are dissolved in deionized water, it is molten that mixing is obtained 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 product is centrifuged, washs, dry after obtain the Al doping ZrO2It is situated between and sees crystal.
2. Al according to claim 1 doping ZrO2It is situated between and sees the preparation method of crystal, it is characterised in that：Step（1）Mixing is molten
The substance withdrawl syndrome of sodium chloride is 0~0.005mol/L in liquid；Aluminum nitrate is with the substance withdrawl syndrome sum of zirconium oxychloride
0.75 mol/L, the amount of the material of aluminum nitrate accounts for the 2%~5% of aluminum nitrate and the amount of zirconium oxychloride total material；The material of urea
Amount concentration is 1.5 mol/L.
3. obtained in a kind of the method for claim 1 Al doping ZrO2It is situated between and sees crystal, it is characterised in that：Pattern is class ball
Shape or disc-shaped；A diameter of 30~100 nm of near-spherical；A diameter of 70~200 nm of disc-shaped, thickness is 30~70 nm；BET
Specific surface area is 160~172 m2/ g, internal porous, most probable pore size is 2 nm.
4. a kind of Al as claimed in claim 3 doping ZrO2It is situated between and sees the application of crystal, it is characterised in that：Water is prepared as carrier
Gas conversion catalyst.
5. Al according to claim 4 doping ZrO2It is situated between and sees the application of crystal, it is characterised in that：Preparation method is：In ultrasound
Under the broken subsidiary conditions of ripple, by Al doping ZrO2The sight crystal that is situated between is scattered in copper nitrate aqueous solution, is then added dropwise thereto
To pH value of solution=9.0, gained precipitates and water gas converting catalyst is obtained after centrifuge washing, drying, roasting alkali lye.
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Citations (3)
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|---|---|---|---|---|
| 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 |
| 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 |
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2017
- 2017-01-25 CN CN201710055913.7A patent/CN106799261B/en not_active Expired - Fee Related
Patent Citations (3)
| 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 |
| 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 |
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| 张燕杰: "CuO/ZrO2水煤气变换催化剂：制备及构效关系研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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