CN114797830B - Cerium-zirconium solid solution with low-temperature catalytic performance and preparation method and application thereof - Google Patents
Cerium-zirconium solid solution with low-temperature catalytic performance and preparation method and application thereof Download PDFInfo
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- CN114797830B CN114797830B CN202210561410.8A CN202210561410A CN114797830B CN 114797830 B CN114797830 B CN 114797830B CN 202210561410 A CN202210561410 A CN 202210561410A CN 114797830 B CN114797830 B CN 114797830B
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- 239000006104 solid solution Substances 0.000 title claims abstract description 56
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 5
- 150000000703 Cerium Chemical class 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 150000003754 zirconium Chemical class 0.000 claims description 18
- 229910052684 Cerium Inorganic materials 0.000 claims description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000003495 polar organic solvent Substances 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000004729 solvothermal method Methods 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 3
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 claims description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000010419 fine particle Substances 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 24
- 238000003756 stirring Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 11
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000005639 Lauric acid Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a cerium-zirconium solid solution with low-temperature catalytic performance, and a preparation method and application thereof. The invention provides a cerium-zirconium solid solution with low-temperature catalytic performance, which is an array structure formed by filament monomers and arranged in a three-dimensional order; the filiform monomer is a filiform structure formed by compounding cerium oxide and zirconium oxide; the length of the filiform monomer is in the micron order. The cerium-zirconium solid solution with low-temperature catalytic performance and the fine particles in the tail gas provided by the invention have good contact efficiency, so that the low-temperature catalytic purification performance of the fine particles is improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a cerium-zirconium solid solution with low-temperature catalytic performance, and a preparation method and application thereof.
Background
The exhaust emission of diesel vehicles is an important source of urban atmospheric pollutants at present and constitutes a great risk for human health. Particularly the large amounts of fine particulate matter emitted by diesel engines, may migrate through the respiratory system into the blood in the body, causing lung and cardiovascular damage. In order to reduce the emission of fine particulate matters, a particle catcher is added in a diesel vehicle exhaust aftertreatment system, but the ignition temperature of the fine particulate matters is usually above 450 ℃ because the temperature of the diesel vehicle exhaust is usually low (generally 200-400 ℃). Thus, to achieve combustion clean-up of fine particulate matter on the particulate matter trap, and thus regeneration of the particulate matter trap, it is necessary to coat the particulate matter trap with a catalyst to promote low-temperature combustion of low particulates.
Cerium-zirconium solid solutions are the most commonly used fine particulate oxidation catalysts, and the contact efficiency of cerium-zirconium solid solutions and fine particulate is a major limiting factor affecting the low-temperature catalytic oxidation of fine particulate.
The cerium-zirconium solid solution in the prior art is a stack of nano particles, has a small pore structure, and has low contact efficiency with fine particles, so that the low-temperature catalytic oxidation performance of the fine particles is poor.
Disclosure of Invention
The invention aims to provide a cerium-zirconium solid solution with low-temperature catalytic performance, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a cerium-zirconium solid solution with low-temperature catalytic performance, which is an array structure formed by filament monomers and arranged in a three-dimensional order;
the filiform monomer is a filiform structure formed by compounding cerium oxide and zirconium oxide;
the length of the filiform monomer is in the micron order.
Preferably, the aspect ratio of the filamentous monomer is 80 to 115:1.
the invention also provides a preparation method of the cerium-zirconium solid solution with low-temperature catalytic performance, which comprises the following steps:
mixing water-soluble cerium salt, water-soluble zirconium salt, a polar organic solvent, a template agent and a structure regulator, and performing solvothermal reaction to obtain a precursor material;
and roasting the precursor material to obtain the cerium-zirconium solid solution with low-temperature catalytic performance.
Preferably, the water-soluble cerium salt comprises one or more of cerium nitrate, ammonium cerium nitrate and cerium chloride;
the water-soluble zirconium salt comprises one or more of zirconium nitrate, zirconium acetate and zirconyl nitrate;
the molar ratio of cerium element in the water-soluble cerium salt to zirconium element in the water-soluble zirconium salt is less than or equal to 7:3.
preferably, the polar organic solvent includes an amide solvent and a monohydric alcohol solvent;
the amide solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-diethylformamide, N-diethylacetamide, N-methylformamide, N-methylacetamide and N-methylpropionamide;
the monohydric alcohol solvent comprises one or more of methanol, ethanol, n-propanol and isopropanol;
the amount of the monohydric alcohol solvent is 19 to 114 times the amount of the cerium element in the water-soluble cerium salt; the amount of the amide solvent is 14.5 to 87 times that of the cerium element in the water-soluble cerium salt.
Preferably, the templating agent includes C 9～15 An alkanoic acid;
the amount of the substance of the template agent is 10 to 90% of the total amount of the substance of cerium element in the water-soluble cerium salt and zirconium element in the water-soluble zirconium salt.
Preferably, the structure modifier comprises ethylene glycol and/or glycerol.
The amount of the substance of the structure-adjusting agent is 15 to 45 times the total amount of the substance of cerium element in the water-soluble cerium salt and zirconium element in the water-soluble zirconium salt.
Preferably, the solvothermal reaction is carried out at a temperature of 120-200 ℃ for 12-60 hours.
Preferably, the roasting temperature is 300-700 ℃, and the heat preservation time is 2-6 h.
The invention also provides application of the cerium-zirconium solid solution with low-temperature catalytic performance in solid catalysis, which is prepared by the preparation method in the technical scheme.
The invention provides a cerium-zirconium solid solution with low-temperature catalytic performance, which is an array structure formed by filament monomers and arranged in a three-dimensional order; the filiform monomer is a filiform structure formed by compounding cerium oxide and zirconium oxide; the length of the filiform monomer is in the micron order. The cerium-zirconium solid solution with low-temperature catalytic performance provided by the invention has a three-dimensional orderly arranged array structure, and has a similar morphology structure with the fiber filament-like structure of the fine particles in the tail gas, so that the fine particles can be better attached to the surface of the cerium-zirconium solid solution, the contact efficiency of the fine particles and the cerium-zirconium solid solution is improved, and the low-temperature catalytic purification performance of the fine particles is further improved.
Drawings
FIG. 1 is an SEM image of a cerium-zirconium solid solution obtained in example 2;
FIG. 2 is an SEM image of the product obtained in comparative example 2;
FIG. 3 is an SEM image of the product obtained in comparative example 3;
FIG. 4 is a TEM image of a cerium-zirconium solid solution obtained in example 2;
FIG. 5 is a TEM image of the product obtained in comparative example 2;
FIG. 6 is a TEM image of the product obtained in comparative example 3;
FIG. 7 is a graph showing pore diameter distribution of cerium-zirconium solid solutions obtained in examples 1 to 4;
FIG. 8 is N of the cerium-zirconium solid solutions obtained in examples 1 to 4 2 -an adsorption-desorption isotherm plot;
FIG. 9 is a graph showing CO generated during the catalysis of fine particles by the cerium-zirconium solid solutions obtained in examples 1 to 4 2 A graph of concentration and catalytic temperature;
FIG. 10 is a graph showing the purification efficiency of the cerium-zirconium solid solutions obtained in examples 1 to 4 with respect to fine particles;
FIG. 11 is a graph showing CO generated during the catalysis of fine particulate matters by the products of comparative examples 1 to 3 2 A graph of concentration and catalytic temperature;
FIG. 12 is a graph showing the purification efficiency of the products of comparative examples 1 to 3 with respect to fine particulate matters.
Detailed Description
The invention provides a cerium-zirconium solid solution with low-temperature catalytic performance, which is an array structure formed by filament monomers and arranged in a three-dimensional order;
the filiform monomer is a filiform structure formed by compounding cerium oxide and zirconium oxide;
the length of the filiform monomer is in the micron order.
In the present invention, the aspect ratio of the filamentous monomer is preferably 80 to 115:1, more preferably 85 to 110:1, more preferably 90 to 105:1, most preferably 95 to 100:1.
the invention also provides a preparation method of the cerium-zirconium solid solution with low-temperature catalytic performance, which comprises the following steps:
mixing water-soluble cerium salt, water-soluble zirconium salt, a polar organic solvent, a template agent and a structure regulator, and performing solvothermal reaction to obtain a precursor material;
and roasting the precursor material to obtain the cerium-zirconium solid solution with low-temperature catalytic performance.
In the present invention, all preparations are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes water-soluble cerium salt, water-soluble zirconium salt, polar organic solvent, template agent and structure regulator, and carries out solvothermal reaction to obtain precursor material.
In the present invention, the water-soluble cerium salt preferably includes one or more of cerium nitrate, ammonium cerium nitrate and cerium chloride. In a specific embodiment of the present invention, the cerium nitrate is specifically Ce (NO 3 ) 3 ·6H 2 O. In the present invention,the water-soluble zirconium salt preferably comprises one or more of zirconium nitrate, zirconium acetate and zirconyl nitrate. In a specific embodiment of the present invention, the zirconium nitrate is specifically Zr (NO 3 ) 4 ·5H 2 O。
In the present invention, the molar ratio of the cerium element in the water-soluble cerium salt and the zirconium element in the water-soluble zirconium salt is preferably 7 or less: 3, more preferably 3: 7-7: 3, more preferably 1:1 to 7:3.
in the present invention, the polar organic solvent preferably includes an amide-based solvent and a monohydric alcohol-based solvent. In the present invention, the amide-based solvent preferably includes one or more of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-diethylformamide, N-diethylacetamide, N-methylformamide, N-methylacetamide and N-methylpropionamide. In the present invention, the monohydric alcohol solvent includes one or more of methanol, ethanol, n-propanol and isopropanol. In the present invention, the volume ratio of the amide-based solvent to the monohydric alcohol-based solvent is preferably 1:1. in the present invention, the amount of the monohydric alcohol solvent is preferably 19 to 114 times, more preferably 30 to 110 times, and even more preferably 40 to 100 times the amount of the cerium element in the water-soluble cerium salt. In the present invention, the amount of the amide-based solvent is preferably 14.5 to 87 times, more preferably 20 to 80 times, and even more preferably 30 to 70 times the amount of the cerium element in the water-soluble cerium salt.
In the present invention, the template preferably includes C 9～15 An alkanoic acid; lauric acid is more preferred. In the present invention, the amount of the substance of the template is preferably 10 to 90%, more preferably 20 to 80%, still more preferably 30 to 70%, and most preferably 40 to 60% of the total amount of the substance of cerium element in the water-soluble cerium salt and zirconium element in the water-soluble zirconium salt.
In the present invention, the structure-adjusting agent preferably includes ethylene glycol and/or glycerol. In the present invention, the amount of the substance of the structure-adjusting agent is preferably 15 to 45 times, more preferably 20 to 40 times, and even more preferably 25 to 35 times the total amount of the substance of cerium element in the water-soluble cerium salt and zirconium element in the water-soluble zirconium salt.
In the present invention, the mixing process is preferably:
primary mixing water-soluble cerium salt, water-soluble zirconium salt and a polar organic solvent to obtain a primary mixture;
mixing the primary mixture with a template agent for the second time to obtain a secondary mixture;
and mixing the secondary mixture with a structure regulator in a tertiary mode to obtain a tertiary mixture.
The primary mixing process is not particularly limited, and the water-soluble cerium salt and the water-soluble zirconium salt can be completely dissolved.
In the present invention, the secondary mixing is preferably performed under stirring; the rotation speed of the stirring is preferably 60 to 1500rpm, more preferably 100 to 1400rpm, still more preferably 200 to 1300rpm; the time is preferably 0.5 to 5.0 hours, more preferably 1.0 to 4.0 hours, and still more preferably 2.0 to 3.0 hours.
In the present invention, the tertiary mixing is preferably performed by dropping the structure-adjusting agent into the secondary mixture. In the present invention, the dropping speed is preferably 3 to 10mL/min, more preferably 5 to 8mL/min. After the completion of the dropping, the present invention further includes continuously stirring the obtained mixture for 5 to 180 minutes, more preferably 20 to 160 minutes, still more preferably 30 to 150 minutes.
In the present invention, the temperature of the solvothermal is preferably 120 to 200 ℃, more preferably 130 to 180 ℃, still more preferably 140 to 170 ℃; the time is preferably 12 to 60 hours, more preferably 15 to 55 hours, and still more preferably 20 to 50 hours. In a specific embodiment of the invention, the solvothermal reaction is preferably carried out in a stainless steel reactor with polytetrafluoroethylene lining. The solution thermal reaction is performed under the above conditions, so that the crystallization process of cerium-zirconium ions can be precisely controlled, and grains of the cerium-zirconium solid solution grow along a specific direction in the crystallization process, thereby obtaining the three-dimensional orderly arranged array structure.
After the solvothermal treatment, the invention also preferably includes sequentially cooling, washing and filtering the resulting material. The process of cooling, washing and filtering is not particularly limited, and may be performed by a process well known to those skilled in the art.
After the precursor material is obtained, the precursor material is roasted to obtain the cerium-zirconium solid solution with low-temperature catalytic performance.
In the present invention, the temperature of the calcination is preferably 300 to 700 ℃, more preferably 350 to 650 ℃, still more preferably 400 to 600 ℃; the heating rate for heating to the roasting temperature is preferably 2-20 ℃/min; the holding time is 2 to 6 hours, more preferably 2.5 to 5.5 hours, still more preferably 3 to 5 hours. In the present invention, the firing is preferably performed in an atmosphere of air or oxygen.
The invention also provides application of the cerium-zirconium solid solution prepared by the technical scheme or the preparation method of the technical scheme in solid catalysis. The present invention is not particularly limited to the specific embodiments of the application, and may be employed as is well known to those skilled in the art.
For further explanation of the present invention, a cerium-zirconium solid solution having low-temperature catalytic performance, a preparation method and application thereof, provided by the present invention, will be described in detail with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
59g Ce (NO) 3 ) 3 ·6H 2 O、25g Zr(NO 3 ) 4 ·5H 2 Mixing O and 712mL of polar organic solvent (wherein the volume ratio of N, N-dimethylformamide to absolute ethanol is 1:1) to obtain a first-stage mixture;
mixing the primary mixture with 4g of lauric acid for 4.5 hours at a stirring speed of 900rpm to obtain a secondary mixture;
dropwise adding 306mL of ethylene glycol into the secondary mixture at a speed of 10mL/min, and continuously stirring for 20min to obtain a tertiary mixture;
placing the tertiary mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing solvothermal reaction for 48 hours at 180 ℃; after the reaction is completed, the obtained materials are sequentially cooled, washed and filtered to obtain a precursor material;
and heating the precursor material to 600 ℃ at a heating rate of 10 ℃/min under the air atmosphere, and preserving the temperature for 3 hours to obtain the cerium-zirconium solid solution.
Example 2
59g Ce (NO) 3 ) 3 ·6H 2 O、25g Zr(NO 3 ) 4 ·5H 2 Mixing O and 712mL of polar organic solvent (wherein the volume ratio of N, N-dimethylformamide to absolute ethanol is 1:1) to obtain a first-stage mixture;
mixing the primary mixture with 12g of lauric acid at a stirring speed of 900rpm for 4.5 hours to obtain a secondary mixture;
dropwise adding 306mL of ethylene glycol into the secondary mixture at a speed of 10mL/min, and continuously stirring for 20min to obtain a tertiary mixture;
placing the tertiary mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing solvothermal reaction for 48 hours at 180 ℃; after the reaction is completed, the obtained materials are sequentially cooled, washed and filtered to obtain a precursor material;
and heating the precursor material to 600 ℃ at a heating rate of 10 ℃/min under the air atmosphere, and preserving the temperature for 3 hours to obtain the cerium-zirconium solid solution.
Example 3
59g Ce (NO) 3 ) 3 ·6H 2 O、25g Zr(NO 3 ) 4 ·5H 2 Mixing O and 712mL of polar organic solvent (wherein the volume ratio of N, N-dimethylformamide to absolute ethanol is 1:1) to obtain a first-stage mixture;
mixing the primary mixture with 24g of lauric acid at a stirring speed of 900rpm for 4.5 hours to obtain a secondary mixture;
dropwise adding 306mL of ethylene glycol into the secondary mixture at a speed of 10mL/min, and continuously stirring for 20min to obtain a tertiary mixture;
placing the tertiary mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing solvothermal reaction for 48 hours at 180 ℃; after the reaction is completed, the obtained materials are sequentially cooled, washed and filtered to obtain a precursor material;
and heating the precursor material to 600 ℃ at a heating rate of 10 ℃/min under the air atmosphere, and preserving the temperature for 3 hours to obtain the cerium-zirconium solid solution.
Example 4
59g Ce (NO) 3 ) 3 ·6H 2 O、25g Zr(NO 3 ) 4 ·5H 2 Mixing O and 712mL of polar organic solvent (wherein the volume ratio of N, N-dimethylformamide to absolute ethanol is 1:1) to obtain a first-stage mixture;
mixing the primary mixture with 36g of lauric acid at a stirring speed of 900rpm for 4.5 hours to obtain a secondary mixture;
dropwise adding 306mL of ethylene glycol into the secondary mixture at a speed of 10mL/min, and continuously stirring for 20min to obtain a tertiary mixture;
placing the tertiary mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing solvothermal reaction for 48 hours at 180 ℃; after the reaction is completed, the obtained materials are sequentially cooled, washed and filtered to obtain a precursor material;
and heating the precursor material to 600 ℃ at a heating rate of 10 ℃/min under the air atmosphere, and preserving the temperature for 3 hours to obtain the cerium-zirconium solid solution.
Comparative example 1
In the form of commercially available Pt/Al 2 O 3 As the catalyst of the fine particulate matter, the loading of Pt was 1wt%.
Comparative example 2
CeO is prepared by adopting a coprecipitation method 2 ；
The preparation method comprises the following steps: 80g Ce (NO) 3 ) 3 ·6H 2 Mixing O with 1500mL pure water, and stirring at 40deg.C for 90min to obtain a mixture A; dropping ammonia water with the concentration of 5% and the mixture A into a beaker together, controlling the pH value of the reaction solution to be 8-9, and stirring the reaction solution at 95 ℃ for 2 hours; after stirring, the reaction solution is cooled, washed and filtered in turn, and the collected product is treated with the following steps of under the air atmosphere,Heating to 600 ℃ and roasting for 3 hours to obtain CeO 2 。
Comparative example 3
CeO is prepared by adopting a coprecipitation method 2 -ZrO 2 ；
The preparation method comprises the following steps:
59g Ce (NO) 3 ) 3 ·6H 2 O、25g Zr(NO 3 ) 4 ·5H 2 Mixing O with 2000mL of pure water, and stirring at 40deg.C for 120min to obtain a mixture A; dropping ammonia water with the concentration of 5% and the mixture A into a beaker together, controlling the pH value of the reaction solution to be 8-9, and stirring the reaction solution for 3h at 90 ℃; after stirring, cooling, washing and filtering the reaction liquid in turn, and roasting the collected product for 3 hours at 600 ℃ under the air atmosphere to obtain CeO 2 -ZrO 2 。
Test example 1
The solid solution of cerium and zirconium obtained in example 2 and the products obtained in comparative examples 2 to 3 were subjected to scanning electron microscopy, the test results are shown in fig. 1 to 3, wherein the SEM image of the solid solution of cerium and zirconium obtained in example 2 is shown in fig. 1, the SEM image of the product obtained in comparative example 2 is shown in fig. 2, and the SEM image of the product obtained in comparative example 3 is shown in fig. 3. As can be seen from fig. 1 to 3, the cerium-zirconium solid solution obtained in the present invention exhibits a three-dimensional ordered array structure composed of filamentous monomers having a length of micrometer scale, whereas the products obtained in comparative example 2 and comparative example 3 are irregular particle aggregates.
Test example 2
The cerium-zirconium solid solution obtained in example 2 and the products obtained in comparative examples 2 to 3 were subjected to transmission electron microscopy, the test results are shown in fig. 4 to 6, wherein the TEM image of the cerium-zirconium solid solution obtained in example 2 is shown in fig. 4, the TEM image of the product obtained in comparative example 2 is shown in fig. 5, and the TEM image of the product obtained in comparative example 3 is shown in fig. 6. As can be seen from fig. 4 to 6, the cerium-zirconium solid solution obtained in the present invention has a nanorod structure composed of nanoparticles, and the products obtained in comparative example 2 and comparative example 3 are irregular agglomerates composed of nanoparticles.
Test example 3
Cerium zirconium obtained in examples 1 to 4The solid solutions were subjected to tests of specific surface area, pore diameter and pore volume, wherein fig. 7 is a pore diameter distribution diagram of the cerium-zirconium solid solutions obtained in examples 1 to 4; FIG. 8 is N of the cerium-zirconium solid solutions obtained in examples 1 to 4 2 -an adsorption-desorption isotherm plot; the test results are shown in table 1;
TABLE 1 Performance test results of cerium zirconium solid solutions obtained in examples 1 to 4
| S BET /(m 2 ·g -1 ) | V total /(cm 3 ·g -1 ) | D pore /nm | |
| Example 1 | 70.84 | 0.17 | 9.36 |
| Example 2 | 73.68 | 0.15 | 8.08 |
| Example 3 | 91.87 | 0.16 | 6.65 |
| Example 4 | 58.11 | 0.13 | 7.34 |
As can be seen from Table 1, the cerium-zirconium solid solution obtained by the invention has rich pore structure and large specific surface area.
Test example 4
The catalyst performance of the catalyst on fine particles was tested by a Temperature Programmed Combustion (TPC) method using the cerium zirconium solid solutions obtained in examples 1 to 4 and the products obtained in comparative examples 1 to 3 as catalysts, while using CO 2 CO of gas analyzer to outlet 2 The gas concentration was measured. The catalyst is dried for 3 hours at the constant temperature of 120 ℃, 270mg of catalyst is taken and ground for 2 minutes, 30mg of fine particles are added for continuous grinding, the catalyst is in close contact with the fine particles, and finally 60mg of ground sample and 120mg of silicon carbide are taken out and uniformly stirred and placed in a metal tube of a catalyst activity evaluation device. Before the test, the mixture is activated for 45 minutes at 160 ℃ under the nitrogen condition, and then O is introduced 2 And is warmed up at a constant warming rate of 5 deg.c/min.
Wherein FIG. 9 is CO generated during the catalysis of the cerium-zirconium solid solutions obtained in examples 1 to 4 2 FIG. 10 is a graph showing the purification efficiency of cerium-zirconium solid solutions obtained in examples 1 to 4 with respect to fine particles, and FIG. 11 is a graph showing the CO generated during the catalytic processes of the products of comparative examples 1 to 3 2 FIG. 12 is a graph showing the purification efficiency of the products of comparative examples 1 to 3 with respect to fine particulate matters; the test results are shown in Table 2
TABLE 2 catalytic Properties of the cerium zirconium solid solutions obtained in examples 1 to 4 and the products obtained in comparative examples 1 to 3
As can be seen from Table 2, the cerium-zirconium solid solution obtained in the present invention is capable of catalyzing the conversion of fine particles in exhaust gas to CO at a lower temperature than that of the comparative example 2 And can make CO in a shorter time 2 The concentration of the cerium-zirconium solid solution reaches the peak value, so that the cerium-zirconium solid solution provided by the invention has higher and faster low-temperature catalytic efficiency on fine particles in tail gas.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (7)
1. The preparation method of the cerium-zirconium solid solution with low-temperature catalytic performance is characterized by comprising the following steps of:
mixing water-soluble cerium salt, water-soluble zirconium salt, a polar organic solvent, a template agent and a structure regulator, and performing solvothermal reaction to obtain a precursor material;
roasting the precursor material to obtain the cerium-zirconium solid solution with low-temperature catalytic performance;
the polar organic solvent comprises an amide solvent and a monohydric alcohol solvent;
the amide solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-diethylformamide, N-diethylacetamide, N-methylformamide, N-methylacetamide and N-methylpropionamide;
the monohydric alcohol solvent comprises one or more of methanol, ethanol, n-propanol and isopropanol;
the template agent comprises C 9～15 An alkanoic acid;
the structure regulator comprises ethylene glycol and/or glycerol;
the temperature of the solvothermal reaction is 120-200 ℃ and the time is 12-60 h;
the cerium-zirconium solid solution is an array structure formed by filament monomers and arranged in a three-dimensional ordered manner;
the filiform monomer is a filiform structure formed by compounding cerium oxide and zirconium oxide;
the length of the filiform monomer is in the micron order.
2. The method of claim 1, wherein the filamentous monomer has an aspect ratio of 80 to 115:1.
3. the preparation method according to claim 1, wherein the water-soluble cerium salt comprises one or more of cerium nitrate, ammonium cerium nitrate and cerium chloride;
the water-soluble zirconium salt comprises one or more of zirconium nitrate, zirconium acetate and zirconyl nitrate;
the molar ratio of cerium element in the water-soluble cerium salt to zirconium element in the water-soluble zirconium salt is less than or equal to 7:3.
4. the production method according to claim 1, wherein the amount of the substance of the monohydric alcohol solvent is 19 to 114 times the amount of the substance of cerium element in the water-soluble cerium salt; the amount of the amide solvent is 14.5 to 87 times that of the cerium element in the water-soluble cerium salt.
5. The production method according to claim 1, wherein the amount of the substance of the template agent is 10 to 90% of the total amount of the substance of cerium element in the water-soluble cerium salt and zirconium element in the water-soluble zirconium salt.
6. The production method according to claim 1, wherein the amount of the substance of the structure-adjusting agent is 15 to 45 times the total amount of the substance of cerium element in the water-soluble cerium salt and zirconium element in the water-soluble zirconium salt.
7. The preparation method according to claim 1, wherein the roasting temperature is 300-700 ℃ and the heat preservation time is 2-6 h.
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