CN115318286A - Platinum catalyst for propane catalytic combustion and preparation method and application thereof - Google Patents
Platinum catalyst for propane catalytic combustion and preparation method and application thereof Download PDFInfo
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- CN115318286A CN115318286A CN202211019329.3A CN202211019329A CN115318286A CN 115318286 A CN115318286 A CN 115318286A CN 202211019329 A CN202211019329 A CN 202211019329A CN 115318286 A CN115318286 A CN 115318286A
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 239000001294 propane Substances 0.000 title claims abstract description 73
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005470 impregnation Methods 0.000 claims abstract description 19
- 238000011068 loading method Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000003980 solgel method Methods 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000010955 niobium Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 241000282326 Felis catus Species 0.000 claims description 8
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 8
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- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- -1 carbon alkane Chemical class 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
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- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
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- 241000894007 species Species 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
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- 229910018879 Pt—Pd Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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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
- B01J23/38—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
- B01J23/6527—Tungsten
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a platinum catalyst for propane catalytic combustion, a preparation method and application thereof, wherein the catalyst is prepared from Nb 2 O 5 The carrier is Pt as an active component, W as an auxiliary agent, the loading amount of Pt is 0.5-2% of the mass of the carrier, and the loading amount of W is 1-15% of the mass of the carrier. Synthesis of Nb by Sol-gel method 2 O 5 Loading a certain content of Pt and W precursor on the surface of a carrier by an isometric co-impregnation method, standing, drying and roasting at high temperature to obtain Pt-xW/Nb 2 O 5 A catalyst. Compared with the prior art, the catalyst has high activity, high thermal stability, water resistance and CO resistance 2 Strong capability and the like, and the preparation method is simple, high in repeatability, environment-friendly and safe.
Description
Technical Field
The invention belongs to the field of atmospheric pollution control, and particularly relates to a platinum catalyst for propane catalytic combustion and a preparation method and application thereof.
Background
The emission of low-carbon alkanes such as methane, propane and butane is increasing due to the exhaust emission of a large amount of liquefied petroleum gas and liquefied natural gas as fuel in the production process of chemical industries such as coal chemical industry and petroleum refining and the exhaust emission of motor vehicles. The low-carbon alkane is a main precursor for near-surface ozone formation, and poses serious threats to human health and natural environment, so that how to control and eliminate the low-carbon alkane emission is also one of the hot spots of research in the environmental field. The catalytic combustion method has the advantages of high purification efficiency, wide concentration of treated waste gas, no secondary pollution, low economic cost and the like, is one of the most effective methods for controlling and eliminating the emission of low-carbon alkane, and has the core of designing and preparing a high-performance catalyst.
Propane is a typical low-carbon alkane, and because of the chemical property of the propane, compared with pollution of aromatic hydrocarbon, aldehyde, acid, chlorinated compounds and the like, the propane molecule is more difficult to catalytically eliminate due to inert and strong C-H bonds. The high-performance catalysts for propane catalytic combustion at present can be mainly classified into Pt, pd and Ru supported noble metal catalysts, co-based and Mn-based transition metals and composite oxide catalysts thereof. Chinese patent (CN 113786835A, CN 113070071A) discloses Co 3 O 4 The base catalyst shows more excellent propane oxidation activity and has lower cost, but the catalyst has complicated preparation process and high energy consumption, can generate a large amount of pollutants such as waste water and the like, and more importantly, co 3 O 4 The active components are easy to sinter at high temperature and are easy to inactivate under the condition of water vapor, and the reduction of catalytic activity is inevitably caused. Sandwich Zr/Pt-Pd/Mg-Al disclosed in Chinese patent CN112958086A 2 O 3 A catalyst,has better hydrothermal stability, but because the active site of Pt-Pd is partially ZrO 2 The protective layer coverage results in a catalyst with poor catalytic oxidation activity for propane. In addition, the document (J.Phys.chem.C 2021,125,19301) reports a Pt/Nb for propane catalytic combustion 2 O 5 The catalyst has the propane full conversion temperature as high as 370 ℃, and can not meet the actual exhaust emission requirement. Chinese patent CN109675556A discloses a CeO prepared by hydrothermal and deposition precipitation methods 2 Nanorod supported Ru catalyst, ru/CeO 2 The excellent propane combustion activity is shown, and the full conversion temperature of the propane can be as low as 190 ℃. However, the preparation process of the catalyst involves the discharge of a large amount of waste alkali liquor, and the production processes of hydrothermal synthesis, high-temperature hydrogen reduction and the like have certain safety risks. More importantly, the active component RuO x The species are constructed by high temperature reduction, and the high temperature stability of the species is to be examined. Therefore, there is a need to develop a high performance catalyst that meets the practical industrial source of propane tail gas emissions abatement.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a platinum catalyst for propane catalytic combustion and a preparation method and application thereof. The catalyst has high activity, high stability, and water and CO resistance 2 Strong capability and the like, simple preparation process, environmental protection, safety and good reproducibility.
The purpose of the invention can be realized by the following technical scheme: a platinum catalyst for catalytic combustion of propane is prepared from Nb 2 O 5 The catalyst is a carrier, pt is an active component, W is an auxiliary agent, the load capacity of Pt accounts for 0.5-2% of the mass of the carrier, and the load capacity of W accounts for 1-15% of the mass of the carrier.
Further, the carrier Nb 2 O 5 The preparation method adopts a sol-gel method, and specifically comprises the following steps: respectively dissolving Nb source and citric acid in deionized water at a certain proportion, heating in 60-100 deg.C water bath under stirring until viscous gel appears, drying in 80-140 deg.C oven for 24-48 hr, baking in 700 deg.C air for 4 hr, heating to raise temperatureThe rate was 4 deg.C/min.
Further, the Nb source includes ammonium niobium oxalate, niobium oxalate and niobium pentachloride, preferably ammonium niobium oxalate.
Further, the Nb source and citric acid are used in a molar ratio of 2:1, 1:1 or 1:2, preferably 1:2.
Further, the loading amount of Pt is 1% of the mass of the carrier, and the loading amount of W is 5% of the mass of the carrier.
A method for preparing a platinum catalyst for propane catalytic combustion, comprising the steps of: grinding Nb 2 O 5 Vacuum heating pretreatment of a carrier, preparing a Pt impregnation liquid and a W impregnation liquid, fully stirring the impregnation liquid and the carrier, uniformly mixing, ultrasonically dispersing for 10-20min at room temperature, standing for 12-24h at room temperature, drying in an oven at 60-100 ℃ for 12-48h, roasting for 4h at 500 ℃ in a flowing air atmosphere at a heating rate of 4 ℃/min, and marking the product as Pt-xW/Nb 2 O 5 。
Further, the preparation of the Pt impregnation liquid is to dissolve soluble salt of Pt into deionized water to prepare the Pt impregnation liquid with the concentration of 0.01-0.1 g/ml;
furthermore, the W steeping fluid is prepared by dissolving soluble salt of W in deionized water to prepare the W steeping fluid with the concentration of 0.01-0.1 g/ml.
Further, the active component and the auxiliary agent are loaded by equal-volume co-impregnation.
The application of the platinum catalyst in the treatment of low-carbon alkane waste gas comprises propane catalytic combustion, the low-temperature activity is high, no by-product is generated in the reaction process, the continuous reaction is carried out for 60 hours at 200 ℃, the activity of the catalyst is kept unchanged, and meanwhile, the catalyst has excellent H resistance 2 O and CO 2 Capacity, cyclic reaction stability and thermal stability. Thus, pt-xW/Nb 2 O 5 The catalyst has good application prospect in the treatment of low-carbon alkane waste gas such as industrial propane and the like.
The reaction conditions of the propane catalytic combustion are as follows: 0.2vol.% C 3 H 8 ,2vol.％O 2 /Ar or 5vol.％ H 2 O, mass space velocity: 80000mL h -1 g cat -1 。
Compared with the prior art, the invention has the following advantages:
(1) Pt-W/Nb of the invention 2 O 5 The catalyst can achieve complete oxidation at 250 ℃ (reaction conditions: 0.2vol.% C) 3 H 8 ,2vol.％O 2 Ar, mass space velocity: 80000mL h -1 g cat -1 ) Even under various severe practical conditions (high moisture and CO) 2 Content, long-term reaction stability, repeated recycling and the like), and the catalyst shows excellent catalytic activity. Further research shows that Pt-5W/Nb 2 O 5 The excellent propane oxidation performance of the catalyst is attributed to WO x Doping enhances Nb 2 O 5 While favoring the formation and stabilization of the metallic Pt species on the support surface, this greatly promotes the dissociation of the C-H bond as the rate-determining step in the propane oxidation reaction. In addition thereto, a strongly acidic oxide WO x Species, also promote the adsorption and activation of propane. In addition, the dissociated hydrocarbon fragment ions are oxidized and dehydrogenated under the attack of active oxygen species rich on the surface of the catalyst to be converted into oxygen-containing species such as propylene, acrylic acid, carbonate and the like, and finally the oxygen-containing species are deeply oxidized into CO 2 And H 2 O, the degradation pathway is a more efficient propane oxidation pathway.
(2) Pt-xW/Nb of the invention 2 O 5 The catalyst is used for propane catalytic combustion reaction, and when the load of W is 5%, pt-5W/Nb 2 O 5 The catalyst shows the optimal propane oxidation activity, and can completely catalyze and oxidize propane into H at the temperature of 250 DEG C 2 O and CO 2 No other by-products were produced (reaction conditions: 0.2vol.% C) 3 H 8 ,2vol.％ O 2 /Ar or 5vol.％H 2 O, mass space velocity: 80000mL h -1 g cat -1 ) And Pt-5W/Nb 2 O 5 The catalyst has excellent reaction stability, thermal stability, water and CO resistance 2 The catalyst has the advantages of strong capability and the like, and meanwhile, the preparation method of the catalyst is simple and feasible, high in repeatability, environment-friendly and safe, and can realize industrial large-scale production.
Drawings
FIG. 1 shows Pt-xW/Nb 2 O 5 Catalytic combustion activity diagram of catalyst propane and CO 2 Yield and selectivity profiles. Specifically, FIG. 1a is a graph of the conversion of propane at different catalyst surfaces as a function of temperature, and FIG. 1b is a graph of CO during the catalytic combustion of propane for different catalysts 2 FIG. 1c is a graph of CO formation during catalytic combustion of propane on different catalysts 2 A selectivity profile of (a);
FIG. 2 shows Pt-5W/Nb in dry and aqueous conditions 2 O 5 The catalyst propane catalyzes the combustion reaction and has cyclic stability; wherein FIG. 2a shows Pt-5W/Nb in dry condition 2 O 5 The cyclic stability test chart of the catalytic combustion reaction of the catalyst propane, and FIG. 2b shows Pt-5W/Nb under the water-containing condition 2 O 5 A test chart of the catalytic combustion reaction cycling stability of the catalyst propane;
FIG. 3 shows the reaction of CO with water 2 Under the condition of Pt-5W/Nb 2 O 5 The catalyst propane catalyzes the combustion and reacts stably for a long time;
FIG. 4 shows the temperature of 200-450 ℃ continuous high-low temperature change couple Pt-5W/Nb 2 O 5 The effect of the reactivity of the catalyst propane oxidation;
FIG. 5 is a graph showing the oxidation activity of propane performed on each of the synthesized samples in example 2.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
a Pt catalyst for propane catalytic combustion and a preparation method thereof comprise the following steps:
Nb 2 O 5 preparation of the carrier:
respectively dissolving ammonium niobium oxalate and citric acid in proportion (the molar ratio of Nb to citric acid is 1:2) in 80ml of deionized water, and heating and stirring in 80 ℃ water bath until the ammonium niobium oxalate and the citric acid begin to appear after the ammonium niobium oxalate and the citric acid are fully dissolvedImmediately placing the reactor in a drying oven at 100 ℃ for drying for 36h to obtain brown yellow solid powder, and finally heating to 700 ℃ at the room temperature at the heating rate of 4 ℃/min for roasting for 5h to obtain white Nb 2 O 5 And (3) powder.
Pt-xW/Nb 2 O 5 Preparation of the catalyst:
1wt.% loading of Pt and 5wt.% loading of W. Taking 1g of Nb 2 O 5 The carrier is mechanically ground and is pretreated by vacuum heating, and fresh platinum nitrate impregnation liquid and ammonium metatungstate impregnation liquid of 0.04g/ml are respectively prepared. Respectively taking 0.25ml of platinum nitrate, 0.5ml of ammonium metatungstate impregnation liquid and Nb 2 O 5 Uniformly mixing the carriers, ultrasonically stirring at room temperature for 15min, standing the sample at room temperature for 12h, drying in an oven at 80 ℃ for 24h, roasting the sample in a tubular heating furnace at 500 ℃ for 4h (air flow rate: 100 ml/min) in the flowing air atmosphere, and heating at a rate of 4 ℃/min to obtain the niobium oxide supported platinum and tungsten catalyst marked as Pt-5W/Nb 2 O 5 。
Respectively synthesizing Pt-1W/Nb by the same preparation method 2 O 5 ，Pt-2W/Nb 2 O 5 ，Pt-10W/Nb 2 O 5 And Pt-15W/Nb 2 O 5 A catalyst.
And (3) testing the performance of the catalyst:
(1) Activity assay
The calcined catalyst was tableted and sieved (40-60 mesh granules were taken) and the propane activity was evaluated in a gas-solid fixed bed microreactor (6 mm internal diameter). The amount of catalyst used was 30mg and the temperature was automatically controlled by a K-type thermocouple. Oxygen with the concentration of 20000ppm is taken as an oxidant, the concentration of propane is 2000ppm, and the space velocity is 80000mL h -1 g cat -1 The reaction pressure was 0.1MPa. The test results are shown in FIG. 1, in which FIG. 1a shows Pt-xW/Nb 2 O 5 The catalytic activity of the catalyst propane in the catalytic combustion is shown in the graph, and Pt-5W/Nb can be seen in the graph 2 O 5 Shows the optimal propane oxidation activity, the total conversion temperature is 250 ℃, and no other byproducts are detected in a gas chromatograph, and CO is generated 2 Generation rate of (as shown in FIG. 1 b)Show) and propane conversion are essentially identical, CO 2 The selectivity of (a) is 100% (as shown in FIG. 1 c). These results show that: propane is completely oxidized to H 2 O and CO 2 And no other by-products are generated.
(2) Stability test
Examine Pt-5W/Nb under dry and aqueous conditions 2 O 5 The catalyst propane catalyzes the combustion reaction and has stable circulation. The specific test process is as follows: composition of the reaction gas under dry conditions: 0.2vol.% C 3 H 8 ,2vol.％O 2 Ar, mass space velocity: 80000mL h -1 g cat -1 ) (ii) a Reaction gas composition under aqueous conditions: 0.2vol.% C 3 H 8 ,2vol.％O 2 /Ar,5vol.％ H 2 O, mass space velocity: 80000mL h -1 g cat -1 ). Wherein, 5vol.% H 2 O-introduction was achieved by pumping 5ml of water from the microsampler into the reaction gas (microsampler internal diameter 10.3mm, injection rate 0.121 ml/h) via a KDS LEGATO 100 microinjection pump. In addition to this, nb 2 O 5 Support preparation process and Pt-5W/Nb 2 O 5 The catalyst preparation process and the catalyst performance evaluation conditions were the same as in example 1, and the results are shown in FIG. 2. FIG. 2a shows Pt-5W/Nb in dry condition 2 O 5 The cyclic stability of the catalytic combustion reaction of the catalyst propane is shown in FIG. 2b, which is Pt-5W/Nb under the condition of water content 2 O 5 The cyclic stability of the catalytic propane combustion reaction can be seen from the figure, and the Pt-5W/Nb can be seen under the reaction conditions of drying or water containing 2 O 5 The oxidation activity of the catalyst for catalyzing propane is basically kept unchanged after the catalyst is continuously recycled for 5 times, which shows that Pt-5W/Nb 2 O 5 The catalyst has good reaction stability.
(3) Long term stability test
Examine in the presence of water or CO 2 Under conditions (evaluation of the catalyst under aqueous conditions, as in the stability test described above; CO content 2 Composition of the reaction gas under the conditions: :0.2vol.% C 3 H 8 ,2vol.％O 2 /Ar，5vol.％CO 2 Mass airspeed: 80000mL·h· -1 g cat -1 )。Pt-5W/Nb 2 O 5 Stability of long-term reaction of propane catalytic combustion catalyst, nb 2 O 5 Support preparation process and Pt-5W/Nb 2 O 5 The catalyst preparation process and the catalyst performance evaluation conditions were the same as in example 1, and the results are shown in FIG. 3, from which CO can be seen 2 Introduction of P-Pt-5W/Nb 2 O 5 The propane oxidation activity of the catalyst had essentially no effect, however, when 5vol.% H was added to the reaction gas 2 O or 5vol.% CO 2 And 5vol.% H 2 In the case of a mixture of O and C 3 H 8 At Pt-5W/Nb 2 O 5 The conversion on the catalyst dropped slightly from the initial 93% to the 89% stage and then remained stable over 40 hours. Furthermore, H is removed 2 O and CO 2 Then, C 3 H 8 The transformation of (2) can be fully restored. These results show that Pt-5W/Nb 2 O 5 The catalyst has good H resistance 2 And (4) O capacity.
(4) Influence of continuous high and low temperature change on catalytic activity
The method examines the Pt-5W/Nb ratio at the continuous high-low temperature change of 200-450 DEG C 2 O 5 The specific test procedure for the influence of the reactivity of the catalyst propane oxidation is as follows: the temperature in the tubular heating furnace was maintained at 200 ℃ by a temperature control device, and the catalyst was allowed to continue to operate at the reaction temperature for 10 hours. Then the reaction temperature was raised to 450 ℃ at a rate of 5 ℃/min. Nb 2 O 5 Support preparation process and Pt-5W/Nb 2 O 5 The catalyst preparation process and the catalyst performance evaluation conditions were the same as in example 1, and the results are shown in FIG. 4, from which it can be seen that the conversion of propane was stably maintained at 38.5% at a reaction temperature of 200 ℃; when the reaction temperature is rapidly raised to 450 ℃, the conversion rate of the propane is immediately raised to 99.9 percent and can be stably maintained. After repeated heating and cooling, the propane oxidation activity of the catalyst is kept unchanged, which shows that the Pt-5W/Nb 2 O 5 The catalyst has good thermal stability.
Example 2
A Pt catalyst for propane catalytic combustion and a preparation method thereof comprise the following steps:
Nb 2 O 5 preparation of the carrier:
proportionally dissolving niobium oxalate and citric acid (the molar ratio of Nb to citric acid is 1:1 in 80ml of deionized water respectively, after the two are fully dissolved, heating and stirring in a water bath at 60 ℃ until viscous gel begins to appear, immediately placing a reactor in an oven at 80 ℃ for drying for 48 hours to obtain brown yellow solid powder, finally heating to 700 ℃ at the room temperature at the heating rate of 4 ℃/min, roasting for 4 hours in air to obtain white Nb 2 O 5 And (3) powder.
Pt-xW/Nb 2 O 5 Preparation of the catalyst:
1wt.% loading of Pt and 5wt.% loading of W. Taking 1g of Nb 2 O 5 The carrier is mechanically ground and is pretreated by vacuum heating, and fresh platinum nitrate impregnation liquid and ammonium metatungstate impregnation liquid of 0.01g/ml are respectively prepared. Respectively taking 1ml of platinum nitrate, 5ml of ammonium metatungstate impregnation liquid and Nb 2 O 5 Uniformly mixing the carriers, ultrasonically stirring for 15min at room temperature, standing the sample for 12h at room temperature, drying the sample in an oven at 80 ℃ for 24h, roasting the sample in a tubular heating furnace at 500 ℃ for 4h (air flow rate: 100 ml/min) in the flowing air atmosphere, and heating at a rate of 4 ℃/min to obtain the niobium oxide supported platinum and tungsten catalyst marked as Pt-5W/Nb 2 O 5 。
Respectively synthesizing 0.5Pt-5W/Nb by the same preparation method 2 O 5 、1.5Pt-5W/Nb 2 O 5 And 2Pt-5W/Nb 2 O 5 Catalyst and the same method is adopted to synthesize Pt/Nb 2 O 5 As comparative example 1, 5W/Nb was synthesized 2 O 5 As comparative example 5.
The results of the tests for propane oxidation activity on each of the above synthetic samples are shown in FIG. 5: 5W/Nb 2 O 5 There was almost no propane oxidation activity at 350 ℃. In addition, we found that the activity of the catalyst gradually increased with the increase of the Pt loading, and that the propane oxidation activity of the catalyst remained substantially unchanged when the Pt loading was more than 1.5%, so that the production cost and oxidation activity of the catalyst were integratedIn view of this, a Pt loading of 1% is the most preferred choice. Meanwhile, pt-5w/Nb synthesized in example 2 2 O 5 The propane oxidation activity of the catalyst is significantly lower than that of Pt-5w/Nb in example 1 2 O 5 Catalyst, which may be related to the ratio of Nb precursor to citric acid complexing agent during support preparation. Thus, pt-5W/Nb 2 O 5 In the preparation process of the catalyst, the precursor of Nb is ammonium niobium oxalate, and the molar ratio of Nb to citric acid is 1:2.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A platinum catalyst for propane catalytic combustion, characterized in that the catalyst is Nb 2 O 5 The carrier is Pt as an active component, W as an auxiliary agent, the loading amount of Pt is 0.5-2% of the mass of the carrier, and the loading amount of W is 1-15% of the mass of the carrier.
2. Platinum catalyst for propane catalytic combustion according to claim 1, characterized in that the support Nb 2 O 5 The preparation method adopts a sol-gel method, and specifically comprises the following steps: respectively dissolving Nb source and citric acid in deionized water according to a certain proportion, after the Nb source and the citric acid are fully dissolved, heating and stirring in a water bath at 60-100 ℃ until viscous gel begins to appear, then placing in an oven at 80-140 ℃ for drying for 24-48h, and finally roasting in air at 700 ℃ for 4-6 h, wherein the heating rate is 4 ℃/min.
3. The platinum catalyst for propane catalytic combustion as claimed in claim 2, wherein the Nb source comprises one of ammonium niobium oxalate, niobium oxalate and niobium pentachloride, preferably ammonium niobium oxalate.
4. Platinum catalyst for propane catalytic combustion according to claim 2, characterized in that the Nb source and citric acid are used in a molar ratio of 2:1, 1:1 or 1:2, preferably 1:2.
5. The platinum catalyst for catalytic combustion of propane according to claim 1, characterized in that the loading of Pt is 1% by mass of the support and the loading of W is 5% by mass of the support.
6. A method of preparing a platinum catalyst for propane catalytic combustion as claimed in claim 1, comprising the steps of: grinding Nb 2 O 5 Vacuum heating pretreatment of a carrier, preparing a Pt impregnation liquid and a W impregnation liquid, fully stirring the impregnation liquid and the carrier, uniformly mixing, ultrasonically dispersing for 10-20min at room temperature, standing for 12-24h at room temperature, drying in an oven at 60-100 ℃ for 12-48h, roasting for 4h at 500 ℃ in a flowing air atmosphere at a heating rate of 4 ℃/min, and marking the product as Pt-xW/Nb 2 O 5 。
7. The platinum catalyst for propane catalytic combustion as claimed in claim 6, wherein the Pt impregnation solution is prepared by dissolving soluble salt of Pt in deionized water to prepare 0.01-0.1g/ml Pt impregnation solution;
the W steeping fluid is prepared by dissolving soluble salt of W in deionized water to prepare the W steeping fluid with the concentration of 0.01-0.1 g/ml.
8. A platinum catalyst for propane catalytic combustion as claimed in claim 6, wherein the active component and the co-agent are supported using co-impregnation of equal volume.
9. Use of a platinum catalyst for propane catalytic combustion according to claim 1, wherein the catalyst is used in low carbon alkane exhaust gas treatment, including propane catalytic combustion.
10. The platinum catalyst for propane catalytic combustion as claimed in claim 1, wherein the reaction conditions of the propane catalytic combustion are:0.2vol.％C 3 H 8 ,2vol.％O 2 /Ar or 5vol.％H 2 o, mass space velocity: 80000mL h -1 g cat -1 。
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| CN116393125A (en) * | 2023-04-16 | 2023-07-07 | 北京化工大学 | Propane dehydrogenation catalyst and preparation method and application thereof |
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