CN114984942B - Catalyst for VOC catalytic combustion and preparation method and application thereof - Google Patents
Catalyst for VOC catalytic combustion and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 50
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 89
- 239000002131 composite material Substances 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000012855 volatile organic compound Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052621 halloysite Inorganic materials 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- 230000001681 protective effect Effects 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 51
- 239000010970 precious metal Substances 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 14
- 229910000420 cerium oxide Inorganic materials 0.000 description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000012018 catalyst precursor Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000012702 metal oxide precursor Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XONMHGLIXCOULQ-UHFFFAOYSA-N [O-2].[Ce+3].[O-2].[Al+3] Chemical compound [O-2].[Ce+3].[O-2].[Al+3] XONMHGLIXCOULQ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B01J35/394—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a preparation method of a catalyst for VOC catalytic combustion, which belongs to the technical field of catalyst preparation and comprises the following steps: firstly, stirring and dissolving two kinds of metal compounds, centrifuging, washing, drying, roasting and other steps to obtain a carrier of metal oxide, filling P atoms by taking sodium hypophosphite as a phosphorus source, adding a noble metal solution into a metal oxide carrier solution, mixing and stirring the two solutions, and finally centrifuging, washing, drying, roasting and other steps to obtain a noble metal powder catalyst taking the metal oxide as the carrier; the prepared noble metal catalyst taking the rare earth metal oxide-metal oxide as the carrier has excellent performance and good low-temperature catalytic oxidation effect on alkanes and aromatic VOC.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a catalyst for VOC catalytic combustion and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) refer to a series of organic compounds with a boiling point of 50-260 ℃ at normal temperature, mainly comprise pollutants such as formaldehyde, ethane, acetone, toluene and the like, are mainly from petrochemical industry, printing and dyeing, printing, painting, papermaking, sewage/garbage treatment, transportation and other industries, have high toxicity and volatility, can form aerosol, ozone, photochemical smog and particulate matters under the irradiation of sunlight, and cause great harm to the atmospheric environment and human health, and are important atmospheric pollutants.
The aromatic VOC mainly comes from the industrial production process, has large discharge amount, is easy to diffuse in the air and is a main species for generating secondary aerosol; but the VOC is a typical industrial VOC because of various types, complex chemical structure and difficult degradation. How to economically and efficiently control the VOC in the atmosphere is the key topic of the current air pollution abatement research, and among a plurality of control technologies (adsorption, membrane separation, plasma, photocatalysis, biodegradation, catalytic oxidation, catalytic combustion, etc.), the catalytic combustion method is considered to be the most effective and potential VOC purification method, and meanwhile, the catalytic combustion method is also the leading edge of the research field of developing high-performance and low-cost catalytic materials and applying to the control of the VOC in the atmospheric environment.
The existing VOC combustion catalyst is mainly a precious metal catalyst represented by platinum (Pt) and palladium (Pd), has excellent catalytic performance and high thermal stability, is not easy to generate secondary pollution, is extremely friendly to the environment, is an ideal VOC removing catalyst, and has higher price; the combustion catalyst mainly made of metal oxide materials is moderate in price, but low in catalytic efficiency and difficult to be applied in large-scale practical application, and therefore, the development of the VOC combustion catalyst with high efficiency and low cost is urgently needed to effectively degrade VOC.
Disclosure of Invention
Aiming at the problems, the invention provides a catalyst for VOC catalytic combustion and a preparation method and application thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a method for preparing a catalyst for catalytic combustion of VOCs, comprising the steps of:
(1) Preparation of composite Carrier
Heating the cerium-aluminum composite metal oxide to 200-1000 ℃ in a mixed flowing atmosphere of hydrogen and argon, roasting for 2-10h at a constant temperature, and cooling to obtain the composite carrier;
(2) Modification of
Placing the composite carrier in the rear area of a tubular atmosphere heating furnace, taking sodium hypophosphite as a phosphorus source, placing the sodium hypophosphite in the front area of the tubular atmosphere heating furnace, taking argon as a flowing carrier gas, passing through the tubular atmosphere heating furnace from front to back, heating the front area of the tubular atmosphere heating furnace to above 250 ℃, keeping the temperature and the carrier gas for heat treatment for 1-30min, cooling, washing a product with absolute ethyl alcohol, and drying to obtain a modified composite metal oxide carrier;
(3) Noble metal loading
Dispersing the modified composite metal oxide carrier in a solvent, adding a chloroplatinic acid salt solution, fully stirring and mixing, then sequentially centrifuging, washing and drying to obtain a load precursor, heating the load precursor to 200-1000 ℃ under a protective atmosphere, carrying out heat preservation roasting for 2-10h, and cooling to obtain the catalyst.
Preferably, the preparation method of the cerium-aluminum composite metal oxide includes the steps of:
weighing cerium salt, dissolving the cerium salt in a solvent to obtain a solution A, drying the solution A at the temperature of 50-90 ℃ for 1-24 hours to obtain a first precursor, heating the solution A to the temperature of 200-1000 ℃ in air, roasting the solution A for 2-10 hours at the temperature, and cooling the solution A to obtain a first product; weighing alumina and dispersing the alumina in a solvent, adding the first product, continuously stirring for 1-50h at room temperature, repeating the operations of centrifuging and washing for a plurality of times, and drying for 1-24h at the temperature of 60-200 ℃ to obtain the cerium-aluminum composite metal oxide.
Preferably, the cerium-aluminum composite metal oxide comprises a halloysite support, and the preparation method of the cerium-aluminum composite metal oxide comprises the following steps:
s1, weighing halloysite micro powder, dispersing the halloysite micro powder in 1-3mol/L sulfuric acid solution according to the liquid-material ratio of 1-2g/100mL, heating to 50-60 ℃, keeping the temperature, stirring for 4-6h, separating precipitates after heat preservation, washing the precipitates with deionized water to be neutral, and performing vacuum drying to obtain expanded halloysite;
s2, weighing the expanded halloysite product obtained in the step S1, dispersing the expanded halloysite product in a solvent, adding cerium salt and aluminum salt according to the ratio, continuously stirring for 1-50h at room temperature, repeating the centrifugation-washing operation for a plurality of times, and drying for 1-24h at 60-200 ℃ to obtain the cerium-aluminum composite metal oxide.
Preferably, the solvent is one or more of deionized water, methanol or ethanol.
Preferably, the cerium salt is cerium nitrate, cerium sulfate, cerium acetate or cerium chloride.
Preferably, the concentration of the solution A is 0.05-1g/mL.
Preferably, the mass ratio of the first product to the alumina is (9-199): 1.
preferably, the heating rate of the heat-preservation roasting is 3-5K/min.
Another object of the present invention is to provide a catalyst prepared by the foregoing preparation method.
The invention further aims to provide application of the catalyst, in particular application to catalytic degradation of VOC in the atmospheric environment.
The beneficial effects of the invention are as follows:
(1) The metal oxide material has a catalytic synergistic effect, can promote the reduction of noble metal in the catalyst and reduce carbon deposition on the surface of the catalyst by modifying and adjusting the structural characteristics and related electronic properties of the catalyst, has certain catalytic removal capacity on VOC in the atmospheric environment, and shows great application potential in the field of atmospheric pollutant elimination 2 ) As typical catalysts and supports, special structural features such as oxygen vacancies and reversible valence state changes (Ce) 3+ /Ce 4+ ) Enhancing the activity and stability of the catalyst, wherein Ce 3+ As Lewis base, the catalyst is favorable for adsorbing and converting pollutants, has excellent catalytic performance, has good low-temperature catalytic oxidation effect on alkanes and aromatic VOC, and can increase the specific surface by taking mixed metal oxide as a carrierThe area, the dispersity of the noble metal is improved, the carbon deposition effect is reduced, and the defect of low specific surface area of single rare earth metal is overcome, so that the carrier can be used for catalyzing VOC degradation together with the noble metal.
(2) On the basis of a cerium oxide-aluminum oxide composite oxide carrier, the oxygen vacancy defect on a carrier material is further promoted through a reducing atmosphere, meanwhile, the stability of the oxygen vacancy defect is improved through phosphorus filling treatment, and the catalytic activity is further improved; the stability of the catalyst is improved by filling heterogeneous phosphorus atoms, and the 3p orbit and the 3d empty orbit of the phosphorus have lone pair electrons, so that the local charge density can be induced and the surface charge state can be adjusted, the electronic structure and the adsorption characteristic of cerium oxide can be adjusted due to the embedding of the phosphorus atoms, the combustion catalytic performance is further improved, the catalyst can still maintain good catalytic combustion performance while reducing the noble metal loading, and the cost is reduced while maintaining high-efficiency catalysis; furthermore, the catalytic activity of the composite halloysite is further improved by taking the composite halloysite as a carrier, and specifically, the halloysite has a unique inner and outer wall charge structure, the outer wall is made of silicon oxide and is negatively charged, the inner wall is made of aluminum oxide and is positively charged, an inner electric field can be formed between the inner wall and the outer wall, the reduction-oxidation state conversion of cerium is promoted, and the catalytic degradation activity is further promoted.
(3) The noble metal catalyst prepared by the invention with the metal oxide-metal oxide as the carrier has good catalytic elimination effect on VOC pollutants in the atmospheric environment, and compared with other noble metal catalysts, the noble metal catalyst prepared by the invention has the advantages of simple preparation method, mild reaction conditions, low cost, good repeatability in experiments and contribution to batch production and application of the catalyst, and the noble metal catalyst prepared by the invention can be synthesized at normal temperature and normal pressure.
Detailed Description
The invention is further described in connection with the following examples.
Example 1
(1) Adding 5.5g of alumina powder into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution B;
(2) After the solution B is centrifuged and washed, the solution B is dried for 12 hours at the temperature of 100 ℃ to obtain a precursor material of a metal oxide complex;
(3) Roasting the metal oxide precursor material for 4h at 500 ℃ in a mixed flowing atmosphere of hydrogen and argon (v/v = 1;
(4) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother liquor (1.8 g/L);
(5) Dissolving 5g of alumina in pure water, stirring for 1 hour, dropwise adding 28mL of solution D, and continuously stirring for 5 hours to obtain solution E;
(6) And (3) centrifuging and washing the solution E, drying at 100 ℃ for 12h to obtain a precious metal powder catalyst precursor material, and roasting the material at 500 ℃ for 5h under protective gas flow to obtain the precious metal powder catalyst with metal alumina as a carrier, wherein the content of the precious metal powder catalyst is 1% Pt/Al.
Example 2
(1) Adding 0.1g of cerous nitrate metal salt into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution A;
(2) After the solution A is centrifugally washed, drying the solution A at 80 ℃ for 12 hours to obtain a precursor of the rare earth metal oxide material;
(3) Roasting the precursor for 5 hours at 500 ℃ in a protective atmosphere to obtain a cerium oxide material;
(4) Adding 5.5g of alumina powder into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution B;
(5) Adding 0.025g of prepared cerium oxide into the solution B, and continuously stirring for 4 hours at room temperature to obtain a solution C;
(6) Centrifuging and washing the solution C, and drying at 100 ℃ for 12 hours to obtain a precursor material of a metal oxide complex;
(7) Roasting the metal oxide precursor material for 4h at 500 ℃ in a mixed flowing atmosphere of hydrogen and argon (v/v = 1;
(8) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother solution (1.8 g/L);
(9) Dispersing 5g of metal oxide complex in pure water, stirring for 1h, dropwise adding 28mL of solution D, and continuously stirring for 5h to obtain solution E;
(10) And (3) centrifuging and washing the solution E, drying at 100 ℃ for 12h to obtain a precious metal powder catalyst precursor material, and roasting the material at 500 ℃ for 5h under protective gas flow to obtain the precious metal powder catalyst taking metal oxide as a carrier, wherein the precious metal powder catalyst has the 1% Pt/0.5-percent Ce/Al.
Example 3
(1) Adding 0.2g of cerous nitrate metal salt into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution A;
(2) After the solution A is centrifugally washed, drying the solution A at 80 ℃ for 12 hours to obtain a precursor of the rare earth metal oxide material;
(3) Roasting the material for 5 hours at 500 ℃ in a protective atmosphere to obtain a cerium oxide material;
(4) Adding 5.5g of alumina powder into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution B;
(5) Adding 0.05g of prepared cerium oxide into the solution B, and continuously stirring for 4 hours at room temperature to obtain a solution C;
(6) Centrifuging and washing the solution C, drying at 100 ℃ for 12h to obtain a precursor material of a metal oxide complex,
(7) Roasting the metal oxide precursor material for 4h at 500 ℃ in a mixed flowing atmosphere of hydrogen and argon (v/v = 1;
(8) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother solution (1.8 g/L);
(9) Dispersing 5g of metal oxide complex in pure water, stirring for 1h, dropwise adding 28mL of solution D, and continuously stirring for 5h to obtain solution E;
(10) And (3) centrifuging and washing the solution E, drying at 100 ℃ for 12h to obtain a precious metal powder catalyst precursor material, and roasting the material at 500 ℃ for 5h under protective gas flow to obtain the precious metal powder catalyst taking metal oxide as a carrier, wherein the precious metal powder catalyst has the 1% Pt/1% Ce/Al.
Example 4
(1) Adding 1g of cerous nitrate metal salt into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution A;
(2) After the solution A is centrifugally washed, drying the solution A at 80 ℃ for 12 hours to obtain a precursor of the rare earth metal oxide material;
(3) Roasting the material for 5 hours at 500 ℃ under the protective atmosphere to obtain a cerium oxide material;
(4) Adding 5.5g of alumina powder into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution B;
(5) Adding 0.26g of prepared cerium oxide into the solution B, and continuously stirring for 4 hours at room temperature to obtain a solution C;
(6) Centrifuging and washing the solution C, drying at 100 ℃ for 12h to obtain a precursor material of a metal oxide complex,
(7) Roasting the metal oxide precursor material for 4h at 500 ℃ in a mixed flowing atmosphere of hydrogen and argon (v/v = 1;
(8) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother liquor (1.8 g/L);
(9) Dispersing 5g of metal oxide complex in pure water, stirring for 1h, dropwise adding 28mL of solution D, and continuously stirring for 5h to obtain solution E;
(10) And (3) centrifuging and washing the solution E, drying at 100 ℃ for 12h to obtain a precious metal powder catalyst precursor material, and roasting the material at 500 ℃ for 5h under protective gas flow to obtain the precious metal powder catalyst taking metal oxide as a carrier, wherein the precious metal powder catalyst has the 1% Pt/5% Ce/Al.
Example 5
(1) Adding 2.1g of cerous nitrate metal salt into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution A;
(2) After the solution A is centrifugally washed, drying the solution A at 80 ℃ for 12 hours to obtain a precursor of the rare earth metal oxide material;
(3) Roasting the material for 5 hours at 500 ℃ under the protective atmosphere to obtain a cerium oxide material;
(4) Adding 5.5g of alumina powder into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution B;
(5) Adding 0.56g of prepared cerium oxide into the solution B, and continuously stirring for 4 hours at room temperature to obtain a solution C;
(6) Centrifuging and washing the solution C, and drying at 100 ℃ for 12h to obtain a precursor material of a metal oxide complex;
(7) Roasting the metal oxide precursor material for 4h at 500 ℃ in a mixed flowing atmosphere of hydrogen and argon (v/v = 1;
(8) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother solution (1.8 g/L);
(9) Dispersing 5g of metal oxide complex in pure water, stirring for 1h, dropwise adding 28mL of solution D, and continuously stirring for 5h to obtain solution E;
(10) Centrifuging and washing the solution E, drying at 100 ℃ for 12 hours to obtain a noble metal powder catalyst precursor material, and calcining the material at 500 ℃ for 5 hours under a protective gas stream to obtain a noble metal powder catalyst supported on metal oxide 1% Pt/10% Ce/Al.
Example 6
(1) Adding 2.1g of cerous nitrate metal salt into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution A;
(2) After the solution A is centrifugally washed, drying the solution A at 80 ℃ for 12 hours to obtain a precursor of the rare earth metal oxide material;
(3) Roasting the material for 5 hours at 500 ℃ under the protective atmosphere to obtain a cerium oxide material;
(4) Adding 5.5g of alumina powder into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution B;
(5) Adding 0.56g of prepared cerium oxide into the solution B, and continuously stirring for 4 hours at room temperature to obtain a solution C;
(6) Centrifuging and washing the solution C, and drying at 100 ℃ for 12h to obtain a precursor material of a metal oxide complex;
(7) Roasting the metal oxide precursor material for 4 hours at 500 ℃ in a flowing atmosphere of argon to obtain a metal-metal oxide complex carrier;
(8) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother solution (1.8 g/L);
(9) Dispersing 5g of metal oxide complex in pure water, stirring for 1h, dropwise adding 28mL of solution D, and continuously stirring for 5h to obtain solution E;
(10) Centrifuging and washing the solution E, drying at 100 ℃ for 12h to obtain a noble metal powder catalyst precursor material, and calcining the material at 500 ℃ for 5h under a protective gas stream to obtain a noble metal powder catalyst supported on metal oxides 1% Pt/10% CeO/AlO.
Example 7
(1) Adding 2.1g of cerous nitrate metal salt into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution A;
(2) After the solution A is centrifugally washed, drying the solution A at 80 ℃ for 12 hours to obtain a precursor of the rare earth metal oxide material;
(3) Roasting the material for 5 hours at 500 ℃ in a protective atmosphere to obtain a cerium oxide material;
(4) Adding 5.5g of alumina powder into pure water, stirring for 5 hours at room temperature, and dissolving to obtain a solution B;
(5) Adding 0.56g of prepared cerium oxide into the solution B, and continuously stirring for 4 hours at room temperature to obtain a solution C;
(6) Centrifuging and washing the solution C, and drying at 100 ℃ for 12 hours to obtain a precursor material of a metal oxide complex;
(7) Roasting the metal oxide precursor material for 4h at 500 ℃ in a mixed flowing atmosphere of hydrogen and argon (v/v = 1;
(8) Placing the combined carrier in the rear area of a tubular atmosphere furnace, taking sodium hypophosphite as a phosphorus source in the front area of the tubular atmosphere furnace, taking argon as flowing carrier gas to pass through the tubular atmosphere furnace from front to back, heating the phosphorus source to the temperature of more than 250 ℃, keeping the temperature and the carrier gas (2 sccm) for treatment for 10min, cooling, washing a product with absolute ethyl alcohol, and drying to obtain the modified composite metal oxide;
(9) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother solution (1.8 g/L);
(10) Dispersing 5g of modified composite metal oxide in pure water, stirring for 1h, dropwise adding 28mL of solution D, and continuously stirring for 5h to obtain solution E;
(11) Centrifuging and washing the solution E, drying at 100 ℃ for 12h to obtain a precious metal powder catalyst precursor material, and roasting the material at 500 ℃ for 5h under a protective gas flow to obtain the precious metal powder catalyst taking metal oxide as a carrier, wherein the precious metal powder catalyst has the 1% Pt/10% CeP/AlP.
Example 8
(1) Weighing halloysite micro powder, dispersing the halloysite micro powder in a sulfuric acid solution of 2mol/L according to the liquid-material ratio of 1g/100mL, heating to 50-60 ℃, keeping the temperature, stirring for 4-6h, separating precipitates after the heat preservation is finished, washing the precipitates with deionized water to be neutral, and performing vacuum drying to obtain expanded halloysite;
(2) Weighing the expanded halloysite product obtained in the step S1, dispersing the expanded halloysite product in pure water, adding cerium salt and aluminum salt according to a ratio, continuously stirring for 4 hours at room temperature, repeating the centrifugation-washing operation for 4 times, and drying for 12 hours at 100 ℃ to obtain a cerium-aluminum composite metal oxide;
(3) Roasting the cerium-aluminum composite metal oxide at 500 ℃ for 4 hours in a mixed flowing atmosphere of hydrogen and argon (v/v = 1;
(4) Placing the combined carrier in the rear area of a tubular atmosphere furnace, taking sodium hypophosphite as a phosphorus source in the front area of the tubular atmosphere furnace, taking argon as flowing carrier gas to pass through the tubular atmosphere furnace from front to back, heating the phosphorus source to the temperature of more than 250 ℃, keeping the temperature and the carrier gas (2 sccm) for treatment for 10min, cooling, washing a product with absolute ethyl alcohol, and drying to obtain the modified composite metal oxide;
(5) Weighing 0.18g of chloroplatinic acid salt to prepare 100mL of solution D as mother liquor (1.8 g/L);
(6) Dispersing 5g of modified composite metal oxide in pure water, stirring for 1h, dropwise adding 28mL of solution D, and continuously stirring for 5h to obtain solution E;
(7) And (3) centrifuging and washing the solution E, drying at 100 ℃ for 12h to obtain a precious metal powder catalyst precursor material, and roasting the material at 500 ℃ for 5h under protective gas flow to obtain the precious metal powder catalyst taking metal oxide as a carrier, wherein the precious metal powder catalyst has the 1% Pt/10% CeP/AlP-HNT.
Examples of the experiments
The invention takes rare earth metal-metal oxide with different proportions as a precursor, prepares a noble metal catalyst taking a metal oxide complex as a carrier through heat treatment and crystallization, and applies the material as the catalyst to the catalytic elimination of VOC in the atmospheric environment, and the related experiments are as follows:
the noble metal catalyst using metal oxide union as carrier obtained in examples 1-8 was applied to the catalytic degradation of benzene in aromatic hydrocarbons VOC, the amount of the catalyst was 0.025g (no halloysite carrier), the concentration of benzene in the reaction gas was 1000ppm, and the space velocity was 62000mL g -1 h -1 The conversion at different catalytic temperatures was determined as follows:
| temperature of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| 100℃ | 0 | 0 | 0 | 0 | 0 | 0.01 | 0.01 | 0.03 |
| 120℃ | 0 | 0.01 | 0.01 | 0.04 | 0.04 | 0.09 | 0.11 | 0.18 |
| 140℃ | 0.05 | 0.06 | 0.10 | 0.14 | 0.14 | 0.22 | 0.27 | 0.37 |
| 160℃ | 0.09 | 0.12 | 0.19 | 0.18 | 0.21 | 0.64 | 0.64 | 0.81 |
| 180℃ | 0.18 | 0.18 | 0.32 | 0.30 | 0.29 | 0.79 | 0.82 | 0.92 |
| 200℃ | 0.33 | 0.35 | 0.43 | 0.44 | 0.43 | 0.97 | 0.98 | 1.00 |
| 220℃ | 0.63 | 0.78 | 0.91 | 0.81 | 0.85 | 1.00 | 1.00 | - |
| 240℃ | 0.86 | 0.94 | 1.00 | 0.99 | 1.00 | - | - | - |
| 260℃ | 0.99 | 1.00 | - | 1.00 | - | - | - | - |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. A preparation method of a catalyst for catalytic combustion of VOCs is characterized by comprising the following steps:
(1) Preparation of composite Carrier
Heating to 200-1000 ℃ in a mixed flowing atmosphere of hydrogen and argon, roasting the cerium-aluminum composite metal oxide for 2-10 hours at a constant temperature, and cooling to obtain the composite carrier;
(2) Modification of
Placing the composite carrier in the rear area of a tubular atmosphere heating furnace, taking sodium hypophosphite as a phosphorus source, placing the sodium hypophosphite in the front area of the tubular atmosphere heating furnace, taking argon as flowing carrier gas, passing through the tubular atmosphere heating furnace from front to back, heating the front area of the tubular atmosphere heating furnace to above 250 ℃, keeping the temperature and the carrier gas for heat treatment for 1-30min, washing the product with absolute ethyl alcohol after cooling, and drying to obtain a modified composite metal oxide carrier;
(3) Noble metal loading
Dispersing the modified composite metal oxide carrier in a solvent, adding a chloroplatinic acid salt solution, fully stirring and mixing, then sequentially centrifuging, washing and drying to obtain a load precursor, heating the load precursor to 200-1000 ℃ under a protective atmosphere, carrying out heat preservation roasting for 2-10h, and cooling to obtain the catalyst;
the cerium-aluminum composite metal oxide comprises a halloysite carrier, and the preparation method of the cerium-aluminum composite metal oxide comprises the following steps:
s1, weighing halloysite micro powder, dispersing the halloysite micro powder into 1-3mol/L sulfuric acid solution according to the liquid-material ratio of 1-2g/100mL, heating to 50-60 ℃, keeping the temperature, stirring for 4-6h, separating precipitates after heat preservation, washing the precipitates to be neutral by deionized water, and performing vacuum drying to obtain expanded halloysite;
s2, weighing the expanded halloysite product obtained in the step S1, dispersing the expanded halloysite product in a solvent, adding cerium salt and aluminum salt according to a ratio, continuously stirring for 1-50h at room temperature, repeating the centrifugation-washing operation for a plurality of times, and drying for 1-24h at 60-200 ℃ to obtain the cerium-aluminum composite metal oxide.
2. The method according to claim 1, wherein the solvent used in step (3) and step S2 is one or more selected from deionized water, methanol, and ethanol.
3. The method of claim 1, wherein the cerium salt is cerium nitrate, cerium sulfate, cerium acetate, or cerium chloride.
4. The method according to claim 1, wherein the temperature-raising rate of the heat-preservation calcination in the steps (1) and (3) is 3-5K/min.
5. A catalyst, characterized by being prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the catalyst of claim 5 for the catalytic degradation of atmospheric VOCs.
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