CN111482171A - Pt-based catalyst for complete oxidation of propane and preparation method thereof - Google Patents
Pt-based catalyst for complete oxidation of propane and preparation method thereof Download PDFInfo
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- CN111482171A CN111482171A CN202010253973.1A CN202010253973A CN111482171A CN 111482171 A CN111482171 A CN 111482171A CN 202010253973 A CN202010253973 A CN 202010253973A CN 111482171 A CN111482171 A CN 111482171A
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000001294 propane Substances 0.000 title claims abstract description 39
- 239000011865 Pt-based catalyst Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title description 15
- 230000003647 oxidation Effects 0.000 title description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 42
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 27
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 5
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 19
- 235000019253 formic acid Nutrition 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 12
- 229940010552 ammonium molybdate Drugs 0.000 description 12
- 235000018660 ammonium molybdate Nutrition 0.000 description 12
- 239000011609 ammonium molybdate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001354 calcination Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- -1 alkane compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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Abstract
The invention discloses a Pt-based catalyst for completely oxidizing propane, which consists of a carrier, a cocatalyst and an active component, wherein the carrier is ZrO2The cocatalyst is MoO3The active component is Pt; the invention also provides a method for preparing the catalyst, which comprises the steps of (1) mixing oxalic acid solution and ammonium molybdate tetrahydrate to obtain solution A; (2) adding Pt (NO) to solution A3)2、ZrO2Formic acid to obtain a mixed solution B; (3) and stirring the mixed solution B, and then sequentially drying and roasting to finally obtain the catalyst. The invention has the advantages that the catalyst capable of catalyzing the propane to be completely oxidized at a lower temperature is obtained, the catalyst has good stability, the preparation method is easy to operate, and the large-scale production can be realized.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a Pt-based catalyst for completely oxidizing propane and a preparation method thereof.
Background
With the rapid advance of industrialization, increasingly prominent environmental problems seriously jeopardize the health development of human beings and society, wherein the harm caused by atmospheric pollution is particularly serious. Volatile organic pollutants (VOCs) are important prerequisites for the formation of photochemical smog and ozone. Therefore, effective treatment of volatile organic pollutants plays a crucial role in human and social health development. The method for treating VOCs is various, and the catalytic combustion method is considered to be one of the most effective methods for eliminating volatile organic compounds due to the advantages of relatively low treatment temperature, low energy consumption, difficult generation of secondary pollution and the like. Of the many volatile organics, alkanes are the most chemically stable and require higher temperatures to fully oxidize them. Therefore, it is a serious challenge to develop a catalyst capable of catalyzing the complete oxidation of alkane at a lower temperature.
At present, the Pt-based catalyst is mainly used for catalyzing and oxidizing alkane with better activity. Propane is a relatively representative species in alkanes and chinese patent CN105214687A discloses a Ru catalyst supported on an alumina support doped with different metals. Firstly, preparing Al doped with Ni, Cu, Mg, Co and Mn by a coprecipitation method2O3The carrier is then impregnated and dried to obtain a series of Ru-based catalysts, and finally the Ru-based catalysts are added into 10% H2And reducing the mixture for 3 hours at 500 ℃ in an-Ar atmosphere for complete oxidation of propane. Wherein 4.5 wt% Ru/NiAl2O4The catalyst activity was the best with the lowest temperature to achieve 90% propane conversion being 232 ℃. When the catalyst is used for catalyzing the oxidation of propane, 10% H is required in advance2And (2) reducing in an Ar atmosphere, and obviously inactivating the catalyst after 0.5% of water vapor is introduced into the reaction atmosphere, so that the application range of the catalyst is limited. Chinese patent CN103990460A discloses a catalyst of transition metal oxide for the complete oxidation of propane. Wherein Co3O4The activity is best, the lowest temperature for propane conversion to 90% is 220 ℃, and the catalyst is only suitable for purification of low concentration alkane compounds. Chinese patent CN107469856A discloses Rh-Pd/Fe3O4-LaF3-CeF3BN catalyst is used for the complete oxidation of propane. The lowest temperature to achieve 99.9% conversion of propane was 275 ℃. Chinese patent CN 107537524A discloses Pt/SnO2/AlF3C catalyst for propane combustion. The complete combustion conversion of propane reached 99.9% at a reaction temperature of 275 ℃. Chinese patent CN109821536A discloses a Pt-V2O5/SnO2-Nb2O5The catalyst is used for the complete oxidation of propane. The lowest temperature to achieve 99.9% conversion of propane is 305 ℃.
In combination with the above catalysts for complete oxidation of propane, some catalysts have a higher temperature when used for complete oxidation of propane, and the activity of the catalyst needs to be improved. The invention provides a Pt-based catalyst for completely oxidizing propane and a preparation method thereof, which can completely oxidize propane at a low temperature and are not very rich in types of catalysts, so that the cost for treating alkane compounds without environmental pollution is reduced in order to enrich the types of catalysts for completely oxidizing propane at a low temperature.
Disclosure of Invention
In order to solve the problems in the prior art, the invention discloses a Pt-based catalyst for completely oxidizing propane and a preparation method thereof, and aims to obtain a catalyst capable of catalyzing the complete oxidation of propane at a lower temperature, and the catalyst has good stability, and the preparation method is easy to operate and can be used for large-scale production.
In order to achieve the purpose, the technical scheme disclosed by the invention is as follows: the invention provides a Pt-based catalyst for completely oxidizing propane, which consists of a carrier, a cocatalyst and an active component, wherein the carrier is ZrO2The cocatalyst is MoO3The active component is Pt;
the raw material of the catalyst is prepared from catalyst precursor Pt (NO)3)2、ZrO2Ammonium molybdate tetrahydrate, oxalic acid and formic acid.
Further, the mass fraction of the active ingredient Pt is ZrO21% by weight of (1), MoO3Is ZrO in mass fraction22-8 wt% of (A), the amount of oxalic acid added being ZrO23% by weight of (a) and formic acid in an amount of ZrO 224 to 7 wt% of the total amount of the components.
Further, said Pt (NO)3)2Concentration of (2)0.0020g/m L, formic acid concentration 0.122g/m L, oxalic acid concentration 0.015g/m L.
The invention also provides a method for preparing the catalyst, which comprises the following steps:
(1) dissolving oxalic acid in distilled water, and adding ammonium molybdate tetrahydrate into the obtained oxalic acid solution to obtain a mixed solution A;
(2) adding Pt (NO) to the mixed solution A3)2Solution, adding ZrO after mixing evenly2And formic acid to obtain a mixed solution B;
(3) and stirring the mixed solution B at 25 ℃ for 3h, drying at 100 ℃ for 5h, and roasting at 500 ℃ for 4h to finally obtain the catalyst.
By combining the technical scheme, the invention has the beneficial effects that: the catalyst of the invention is adopted to ensure that the temperature required by the complete oxidation of propane is 245-270 ℃, namely the propane can realize 99.9 percent conversion at lower temperature, the catalyst has good stability, the raw materials for preparing the catalyst of the invention are easy to obtain, and the operation conditions in the preparation method are easy to realize, therefore, the method for preparing the catalyst of the invention has low cost and easy operation, and is easy to realize large-scale production.
Drawings
FIG. 1 shows Pt-6MoO in example 33/ZrO2Stability test chart of catalyst.
Detailed Description
The present invention is described in further detail below with reference to specific examples. The operation of the present invention is prior art without specific mention.
The first embodiment is as follows: pt-2MoO3/ZrO2Catalyst preparation
ZrO on a carrier in terms of Pt mass fraction21 wt% of; MoO3Is ZrO of carrier22 wt% of (B). 0.0300g (ZrO) is weighed23 wt%) oxalic acid, 2m L distilled water, 0.1717g ammonium molybdate was weighed and dissolved in the oxalic acid solution, and 5m L Pt (NO) with a concentration of 0.0020g/m L was weighed3)2Solutions ofMixing uniformly, adding 1.0000g ZrO2Support and 0.41m L (ZrO)25 wt%) 0.122g/m L, magnetically stirring at 25 deg.C for 3 hours, drying at 100 deg.C for 5 hours in an oven, grinding, and calcining at 500 deg.C in a muffle furnace for 4 hours to obtain Pt-2MoO3/ZrO2A catalyst.
Example two: pt-4MoO3/ZrO2Catalyst preparation
ZrO on a carrier in terms of Pt mass fraction21 wt% of; MoO3Is ZrO of carrier2Weighing 0.0300g oxalic acid, adding 2m L distilled water, weighing 0.3434g ammonium molybdate to dissolve in the oxalic acid solution, then weighing 5m L Pt (NO) with concentration of 0.0020g/m L3)2Mixing the solution uniformly, adding 1.0000g ZrO2The carrier and 0.41m L formic acid with concentration of 0.122g/m L are magnetically stirred for 3 hours at 25 ℃, dried for 5 hours in a baking oven at 100 ℃, ground and then placed in a muffle furnace air atmosphere for baking for 4 hours at 500 ℃ to obtain Pt-4MoO3/ZrO2A catalyst.
Example three: pt-6MoO3/ZrO2Catalyst preparation
ZrO on a carrier in terms of Pt mass fraction21 wt% of; MoO3Is ZrO of carrier2Weighing 0.0300g oxalic acid, adding 2m L distilled water, weighing 0.5152g ammonium molybdate to dissolve in the oxalic acid solution, then weighing 5m L Pt (NO) with concentration of 0.0020g/m L3)2Mixing the solution uniformly, adding 1.0000g ZrO2The carrier and 0.41m L formic acid with concentration of 0.122g/m L are magnetically stirred for 3 hours at 25 ℃, dried for 5 hours in a baking oven at 100 ℃, ground and then placed in a muffle furnace air atmosphere for baking for 4 hours at 500 ℃ to obtain Pt-6MoO3/ZrO2A catalyst.
Example four: pt-8MoO3/ZrO2Catalyst preparation
ZrO on a carrier in terms of Pt mass fraction21 wt% of; MoO3Is ZrO of carrier2Weighing 0.0300g oxalic acid, adding 2m L distilled water, weighing 0.6869g ammonium molybdate, dissolving in the oxalic acid solution, weighing 5m L, and concentratingPt (NO) with a degree of 0.0020g/m L3)2Mixing the solution uniformly, adding 1.0000g ZrO2The carrier and 0.41m L formic acid with concentration of 0.122g/m L are magnetically stirred for 3 hours at 25 ℃, dried for 5 hours in a baking oven at 100 ℃, ground and then placed in a muffle furnace air atmosphere for baking for 4 hours at 500 ℃ to obtain Pt-8MoO3/ZrO2A catalyst.
Example five: pt-6MoO3/ZrO2Catalyst preparation
ZrO on a carrier in terms of Pt mass fraction21 wt% of; MoO3Is ZrO of carrier2Weighing 0.0300g oxalic acid, adding 2m L distilled water, weighing 0.5152g ammonium molybdate to dissolve in the oxalic acid solution, then weighing 5m L Pt (NO) with concentration of 0.0020g/m L3)2Mixing the solution uniformly, adding 1.0000g ZrO2Support and 0.33m L (ZrO)24 wt%) formic acid with a concentration of 0.122g/m L, magnetically stirred at 25 ℃ for 3 hours, dried in an oven at 100 ℃ for 5 hours, ground and then calcined in a muffle furnace at 500 ℃ for 4 hours to obtain Pt-6MoO3/ZrO2A catalyst.
Example six: pt-6MoO3/ZrO2Catalyst preparation
ZrO on a carrier in terms of Pt mass fraction21 wt% of; MoO3Is ZrO of carrier2Weighing 0.0300g oxalic acid, adding 2m L distilled water, weighing 0.5152g ammonium molybdate to dissolve in the oxalic acid solution, then weighing 5m L Pt (NO) with concentration of 0.0020g/m L3)2Mixing the solution uniformly, adding 1.0000g ZrO2Support and 0.49m L (ZrO)26 wt%) formic acid with concentration of 0.122g/m L, magnetically stirring at 25 deg.C for 3 hours, drying at 100 deg.C for 5 hours in an oven, grinding, and calcining at 500 deg.C in a muffle furnace for 4 hours to obtain Pt-6MoO3/ZrO2A catalyst.
Example seven: pt-6MoO3/ZrO2Catalyst preparation
ZrO on a carrier in terms of Pt mass fraction21 wt% of; MoO3Is ZrO of carrier26 wt% of (B). Weighing 0.0300g oxalic acid, adding 2mL distilled water, 0.5152g ammonium molybdate is weighed and dissolved in the oxalic acid solution, and then 5m L Pt (NO) with the concentration of 0.0020g/m L is weighed3)2Mixing the solution uniformly, adding 1.0000g ZrO2Support and 0.57m L (ZrO)27 wt%) 0.122g/m L, magnetically stirring at 25 deg.C for 3 hours, drying at 100 deg.C for 5 hours in an oven, grinding, and calcining at 500 deg.C in a muffle furnace for 4 hours to obtain Pt-6MoO3/ZrO2A catalyst.
To illustrate the beneficial effects of the present invention, comparative examples were set up as follows for experimental illustration:
comparative example 1:
adding 2m L distilled water into an evaporating dish, and heating to 60 ℃, wherein ZrO is taken as a carrier according to the mass fraction of Pt21 wt% of; MoO3Is ZrO of carrier2Weighing 0.5152g ammonium molybdate, dissolving in distilled water, cooling to room temperature, and weighing 5m L Pt (NO) with concentration of 0.0020g/m L3)2Mixing the solution uniformly, adding 1.0000g ZrO2Support and 0.41m L (ZrO)25 wt%) 0.122g/m L, magnetically stirring at 25 deg.C for 3 hours, drying at 100 deg.C for 5 hours in an oven, grinding, and calcining at 500 deg.C in a muffle furnace for 4 hours to obtain Pt-6MoO3/ZrO2A catalyst.
Comparative example 2:
adding 2m L distilled water into an evaporating dish, weighing 0.0300g oxalic acid in the evaporating dish, dissolving ZrO taking mass fraction of Pt as a carrier21 wt% of; MoO3Is ZrO of carrier20.5152g of ammonium molybdate were weighed and dissolved in the oxalic acid solution, and 5m of Pt (NO) L with a concentration of 0.0020g/m L was weighed3)2Mixing the solution uniformly, adding 1.0000g ZrO2And (3) a carrier. Magnetically stirring at 25 deg.C for 3 hr, drying in oven at 100 deg.C for 5 hr, grinding, and calcining in muffle furnace at 500 deg.C for 4 hr to obtain Pt-6MoO3/ZrO2A catalyst.
Comparative example 3:
(1) adding 2m L distilled water into evaporation dish, weighing 0.0300g oxalic acid in the evaporation dish, dissolving, and dissolving according to Pt mass fraction of the carrier ZrO21 wt% of; MoO3Is ZrO of carrier20.5152g of ammonium molybdate were weighed and dissolved in the oxalic acid solution, and 5m of Pt (NO) L with a concentration of 0.0020g/m L was weighed3)2Mixing the solution uniformly, adding 1.0000g ZrO2And (3) a carrier. Magnetically stirring at 25 deg.C for 3 hr, drying in oven at 100 deg.C for 5 hr, grinding, and calcining at 500 deg.C in muffle furnace for 4 hr.
(2) 2m L of distilled water were measured out of an evaporation dish, and 0.41m L (ZrO 2) was added25 wt%) formic acid with a concentration of 0.122g/m L, mixing well, weighing 1.0700g of Pt-6MoO prepared in step 13/ZrO2The catalyst was placed in formic acid. Magnetically stirring at 25 deg.C for 3 hr, evaporating in 90 deg.C water bath, and drying in 100 deg.C oven for 5 hr to obtain Pt-6MoO3/ZrO2A catalyst.
The catalysts prepared in examples 1 to 7 and comparative examples 1 to 3 were subjected to catalyst performance tests:
the catalytic performance evaluation of the catalyst is carried out in a fixed bed micro reaction device, the catalyst is subjected to tabletting, 60-80-mesh particles are screened out, and the particles are filled into a quartz tube with the inner diameter of 6mm, and the dosage of the catalyst is 50 mg. The reaction raw material gas is 0.2 percent of C3H8+2％O2+97.8％N2Its space velocity is 80000m L g-1·h-1The flow rate of the corresponding reaction gas was 66.66m L. min-1. The activity of the catalyst is measured as the minimum reaction temperature T at which the conversion is 50% and 99.9%50And T99.9The catalyst reaction performance is shown in tables 1 and 2.
Table 1: reactivity to propane catalytic Oxidation reaction in examples 1-7 (T)50Temperature at 50% conversion of propane, T99.9: temperature of propane conversion 99.9%)
Table 2: reactivity (T) for propane catalytic oxidation reaction in example 3 and comparative examples 1 to 350Temperature at 50% conversion of propane, T99.9: temperature of propane conversion 99.9%)
As can be seen from Table 1, the catalysts of examples 1-7 all exhibited high propane oxidation activity. The catalyst of example 3 has the highest activity, and the conversion rate of propane reaches 99.9% at 245 ℃. As can be seen from comparative examples 1 to 3, if the catalyst lacks oxalic acid and formic acid during impregnation, the catalytic performance of the catalyst is degraded. As can be seen from comparative example 1, the catalyst prepared by dissolving ammonium molybdate with oxalic acid solution is superior to the catalyst prepared by dissolving ammonium molybdate by heating; as can be seen from comparative example 2, the prepared catalyst lacks formic acid reduction during impregnation, and the performance of the prepared catalyst is reduced; it can be seen from comparative example 3 that the reduction of the catalyst with formic acid after calcination is significantly less active than the reduction with formic acid added during impregnation.
Pt-6MoO from example 33/ZrO2The stability of the catalyst was tested (it should be noted that the stability of the catalyst obtained in the other examples is consistent, but the three-phase ratio of the catalyst is different from that of the examples, but the general trend is consistent, so for the sake of brevity, the data of the other examples are not mentioned), the temperature is controlled at 220 ℃, and the stability of the catalyst to the catalytic oxidation of propane is obtained as shown in fig. 1: the catalytic activity at the beginning of the catalyst was 83.3%, and the conversion of propane remained unchanged after 100 hours of reaction, indicating that the stability of the catalyst was very good. In summary, the catalyst Pt-6MoO3/ZrO2The catalyst has high catalytic oxidation activity on propane, good stability and simple preparation process.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The Pt-based catalyst for completely oxidizing propane is characterized by consisting of a carrier, a cocatalyst and an active ingredient, wherein the carrier is ZrO, and the catalyst is prepared from the ZrO2The cocatalyst is MoO3The active component is Pt;
the raw material of the catalyst is prepared from catalyst precursor Pt (NO)3)2、ZrO2Ammonium molybdate tetrahydrate, oxalic acid and formic acid.
2. The catalyst according to claim 1, wherein the mass fraction of the active component Pt is ZrO21% by weight of (1), MoO3Is ZrO in mass fraction22-8 wt% of (A), the amount of oxalic acid added being ZrO23% by weight of (a) and formic acid in an amount of ZrO 224 to 7 wt% of the catalyst.
3. The catalyst of claim 1, wherein the Pt (NO) is3)2Has a concentration of 0.0020g/m L, a concentration of formic acid of 0.122g/m L, and a concentration of oxalic acid of 0.015g/m L.
4. A process for preparing a catalyst according to any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) dissolving oxalic acid in distilled water, and adding ammonium molybdate tetrahydrate into the obtained oxalic acid solution to obtain a mixed solution A;
(2) adding Pt (NO) to the mixed solution A3)2Solution, adding ZrO after mixing evenly2And formic acid to obtain a mixed solution B;
(3) and stirring the mixed solution B at 25 ℃ for 3h, drying at 100 ℃ for 5h, and roasting at 500 ℃ for 4h to finally obtain the catalyst.
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| CN115487832A (en) * | 2022-09-05 | 2022-12-20 | 华东理工大学 | Catalyst for low-temperature propane oxidation and preparation method thereof |
| CN115487832B (en) * | 2022-09-05 | 2024-04-02 | 华东理工大学 | Catalyst for low-temperature propane oxidation and preparation method thereof |
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