CN115318286B - Platinum catalyst for catalytic combustion of propane and preparation method and application thereof - Google Patents
Platinum catalyst for catalytic combustion of propane and preparation method and application thereof Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 239000001294 propane Substances 0.000 title claims abstract description 68
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000011068 loading method Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 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 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 241000282326 Felis catus Species 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 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 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000010955 niobium Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 14
- 230000010718 Oxidation Activity Effects 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 241000894007 species Species 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910018879 Pt—Pd Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 hydrocarbon fragment ions Chemical class 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
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 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
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 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
- 239000011241 protective layer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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 catalytic combustion of propane, a preparation method and application thereof, wherein the catalyst uses Nb 2 O 5 The catalyst is a carrier, pt is an active component, W is an auxiliary agent, the loading of Pt is 0.5-2% of the mass of the carrier, and the loading of W is 1-15% of the mass of the carrier. Synthesis of Nb by sol-gel method 2 O 5 The carrier is loaded with a certain content of Pt and W precursor on the surface of the carrier by an isovolumetric co-impregnation method, and then the Pt-xW/Nb is obtained by standing, drying and high-temperature air roasting 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, simple preparation method, high repeatability, environmental protection and safety.
Description
Technical Field
The invention belongs to the field of air pollution control, and particularly relates to a platinum catalyst for catalytic combustion of propane, and a preparation method and application thereof.
Background
Waste gas emission in the chemical industry generation process of coal chemical industry, petroleum refining and the like and the tail gas emission of a large amount of motor vehicles taking liquefied petroleum gas and liquefied natural gas as fuel, so that the emission of low-carbon alkanes such as methane, propane, butane and the like is increased increasingly. These lower alkanes are the main precursors for near-surface ozone formation, pose serious threats to human health and natural environment, and therefore how to control and eliminate lower alkane emissions is also one of the hot spots of environmental research. The catalytic combustion method has the advantages of high purification efficiency, wide concentration of treated waste gas, no secondary pollution, lower 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 lower alkane, and because of its relatively inert nature and strong C-H bonds, propane molecules are more difficult to catalytically eliminate than aromatics, aldehydes, acids, chlorinated compounds, and the like. The high-performance catalysts used for catalytic combustion of propane at present can be mainly divided into Pt, pd and Ru supported noble metal catalysts, co-based and Mn-based transition metals and composite oxide catalysts thereof. Co disclosed in Chinese patent (CN 113786835A, CN 113070071A) 3 O 4 The base catalyst shows excellent propane oxidation activity and low cost, but the catalyst has the advantages of complex preparation process, high energy consumption, capability of generating a large amount of pollutants such as wastewater, and more importantly Co 3 O 4 The active component is easy to sinter at high temperature and is easy to deactivate under the condition of water vapor, and the catalytic activity is inevitably reduced. Sandwich Zr/Pt-Pd/Mg-Al disclosed in Chinese patent CN112958086A 2 O 3 The catalyst has better hydrothermal stability, but because the Pt-Pd active site is partially coated with ZrO 2 The protective layer coverage results in a catalyst with poor catalytic oxidation activity for propane. In addition, document (J.Phys.chem.C 2021,125,19301) reports a Pt/Nb for propane catalytic combustion 2 O 5 The catalyst, however, the total conversion temperature of propane of the catalyst is as high as 370 ℃, and the actual exhaust emission requirement can not be met. Chinese patent CN109675556A discloses a CeO prepared by hydrothermal and sedimentation 2 Ru catalyst loaded by nano rod, ru/CeO 2 Exhibits excellent propane combustion activity, and the total conversion temperature of the propane can be as low as 190 ℃. However, the preparation process of the catalyst involves a large amount of waste alkali liquid discharge, and the production processes of hydrothermal synthesis, high-temperature hydrogen reduction and the like have certain safety risks. More importantly due to the RuO active ingredient x The species is constructed by high temperature reduction, and the high temperature stability is to be checked. Therefore, there is a need to develop a high performance catalyst that satisfies the practical industrial source propane tail gas emission abatement.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a platinum catalyst for catalytic combustion of propane, a preparation method and application thereof. The catalyst has high activity, high stability, water resistance and CO resistance 2 Strong capability, simple preparation process, environmental protection, safety and good reproducibility.
The aim of the invention can be achieved by the following technical scheme: a Pt 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 loading of Pt is 0.5-2% of the mass of the carrier, and the loading of W is 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 according to a certain proportion, heating and stirring in a water bath at 60-100 ℃ until viscous gel appears, drying in an oven at 80-140 ℃ for 24-48h, and finally roasting in air at 700 ℃ for 4h, wherein the heating rate is 4 ℃/min.
Further, the Nb source includes niobium ammonium oxalate, niobium oxalate and niobium pentachloride, preferably niobium ammonium 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 of Pt is 1% of the mass of the carrier, and the loading of W is 5% of the mass of the carrier.
A method for preparing a platinum catalyst for catalytic combustion of propane, comprising the steps of: grinding Nb 2 O 5 Pretreating the carrier by vacuum heating, preparing Pt impregnating solution and W impregnating solution, fully stirring the impregnating solution and the carrier, uniformly mixing, performing ultrasonic dispersion at room temperature for 10-20min, standing at room temperature for 12-24h, drying in an oven at 60-100 ℃ for 12-48h, finally roasting at 500 ℃ for 4h in flowing air atmosphere, and marking the product as Pt-xW/Nb at a heating rate of 4 ℃/min 2 O 5 。
Further, the preparation of the Pt impregnating solution is to dissolve soluble salt of Pt in deionized water to prepare 0.01-0.1g/ml of Pt impregnating solution;
further, the preparation of the W impregnating solution is to dissolve soluble salt of W in deionized water to prepare 0.01-0.1g/ml of the W impregnating solution.
Further, the active component and the auxiliary agent are loaded by adopting equal volume co-impregnation.
The application of the platinum catalyst is that the catalyst is used in the treatment of low-carbon alkane waste gas, including propane catalytic combustion, the low-temperature activity is high, no by-product is generated in the reaction process, the reaction is carried out continuously for 60 hours at 200 ℃, the activity of the catalyst is kept unchanged, and the catalyst has excellent H resistance 2 O and CO 2 Ability, 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 source propane.
The reaction conditions of the catalytic combustion of propane 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 realize complete oxidation at 250 ℃ (reaction condition: 0.2vol.% C) 3 H 8 ,2vol.％O 2 Ar, mass space velocity: 80000mL h · -1 g cat -1 ) I.e.Simulation under various severe actual conditions (high water vapor and CO 2 Content, long-term reaction stability, repeated use, etc.), the catalyst shows excellent catalytic activity. Further studies have found 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 metallic Pt species on the support surface, which greatly promotes dissociation of C-H bonds as a step-determining step in the propane oxidation reaction. In addition to this, the strongly acidic oxide WO x Species, also promote adsorption and activation of propane. In addition, the dissociated hydrocarbon fragment ions are oxidized and dehydrogenated to be converted into oxygen-containing species such as propylene, acrylic acid, carbonate and the like under the attack of active oxygen species rich in the surface of the catalyst, and finally 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 formed (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, heat stability, water resistance and CO resistance 2 The preparation method of the catalyst is simple and feasible, has high repeatability, is environment-friendly and safe, and can realize industrialized mass production.
Drawings
FIG. 1 is a diagram of Pt-xW/Nb 2 O 5 Catalytic combustion activity diagram of propane and CO 2 Yield and selectivity. Specifically, FIG. 1a is a graph of the conversion of propane with temperature at the surface of different catalysts, and FIG. 1b is a graph of the CO of different catalysts during catalytic combustion of propane 2 FIG. 1c is a graph showing the production rate of propane catalyzed reaction over different catalystsCO in the combustion process 2 Is a selective graph of (2);
FIG. 2 is a graph of Pt-5W/Nb under dry and aqueous conditions 2 O 5 The catalyst propane catalytic combustion reaction cycle stability; wherein FIG. 2a is a diagram of Pt-5W/Nb in dry condition 2 O 5 Catalyst propane catalytic combustion reaction cycle stability test chart, FIG. 2b is Pt-5W/Nb under aqueous conditions 2 O 5 A catalyst propane catalytic combustion reaction cycle stability test chart;
FIG. 3 is a schematic illustration of the composition in aqueous or CO 2 Under the condition of Pt-5W/Nb 2 O 5 The catalyst propane is catalytically combusted for long-time reaction stability;
FIG. 4 shows a continuous temperature change of 200-450 ℃ for Pt-5W/Nb 2 O 5 Influence of the reactivity of the catalyst propane oxidation;
FIG. 5 is a graph showing the propane oxidative activity test performed on each synthetic sample in example 2.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1:
a Pt catalyst for catalytic combustion of propane 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 80ml deionized water according to a proportion (the molar ratio of Nb to citric acid is 1:2), heating and stirring in a water bath at 80 ℃ until viscous gel appears after the ammonium niobium oxalate and the citric acid are fully dissolved, immediately placing the reactor in a 100 ℃ oven for drying for 36 hours to obtain brown yellow solid powder, and finally heating to 700 ℃ at a heating rate of 4 ℃/min at room temperature for 5 hours for roasting in air to obtain white Nb 2 O 5 And (3) powder.
Pt-xW/Nb 2 O 5 Preparation of the catalyst:
the loading of W was 5wt.% based on 1wt.% of Pt loading.Taking 1g Nb 2 O 5 The carrier was mechanically ground and pretreated by vacuum heating, and 0.04g/ml of a fresh platinum nitrate impregnation solution and 0.1g/ml of an ammonium metatungstate impregnation solution were prepared, respectively. Respectively taking 0.25ml of platinum nitrate, 0.5ml of ammonium metatungstate impregnating solution and Nb 2 O 5 Uniformly mixing the carrier, 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 at 500 ℃ for 4h (air flow rate: 100 ml/min) in a tubular heating furnace at a heating rate of 4 ℃/min to obtain the niobium oxide loaded platinum and tungsten catalyst marked as Pt-5W/Nb 2 O 5 。
The same preparation method is adopted to respectively synthesize Pt-1W/Nb 2 O 5 ，Pt-2W/Nb 2 O 5 ，Pt-10W/Nb 2 O 5 And Pt-15W/Nb 2 O 5 A catalyst.
Catalyst performance test:
(1) Activity test
The calcined catalyst was tabletted, sieved (40-60 mesh particles were taken) and evaluated for propane activity using a gas-solid fixed bed microreactor (inner diameter 6 mm). The dosage of the catalyst is 30mg, and the temperature is automatically controlled by a K-type thermocouple. The oxygen with the concentration of 20000ppm is taken as an oxidant, the concentration of propane is 2000ppm, and the airspeed is 80000 mL.h.) -1 g cat -1 The reaction pressure was 0.1MPa. The test results are shown in FIG. 1, FIG. 1a is Pt-xW/Nb 2 O 5 The catalytic combustion activity of propane in the catalyst is shown in the cluster, pt-5W/Nb 2 O 5 Exhibits optimal propane oxidation activity at a full conversion temperature of 250 ℃ and no other byproducts are detected in the gas chromatograph, while CO 2 Is substantially the same as the conversion of propane, CO 2 The selectivity of (a) is 100% (as shown in figure 1 c). These results indicate that: the propane is completely oxidized to H 2 O and CO 2 No other by-products were formed.
(2) Stability test
Under the conditions of drying and water content, pt-5W/Nb was examined 2 O 5 Catalytic propane combustionReaction cycle stability. The specific test procedure is as follows: reaction gas composition under dry conditions: 0.2vol.% C 3 H 8 ,2vol.％O 2 Ar, mass space velocity: 80000mL h · -1 g cat -1 ) The method comprises the steps of carrying out a first treatment on the surface of the 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 was introduced by pumping 5ml of water of the microinjector into the reaction gas (the inner diameter of the microinjector 10.3mm, injection rate 0.121 ml/h) by a KDS LEGATO 100 microinjection pump. In addition to Nb 2 O 5 Carrier 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 Catalyst propane catalytic combustion reaction cycle stability, FIG. 2b is Pt-5W/Nb under aqueous conditions 2 O 5 The catalyst propane catalytic combustion reaction cycle stability, as can be seen from the figure, pt-5W/Nb under either dry or aqueous reaction conditions 2 O 5 The catalytic propane oxidation activity of the catalyst is basically unchanged after the catalyst is circularly used for 5 times continuously, which shows that Pt-5W/Nb 2 O 5 The catalyst has good reaction stability.
(3) Long time stability test
Investigating in water or CO 2 Under conditions (evaluation of the catalyst under aqueous conditions as in the stability test described above; CO-containing) 2 Composition of the reaction gas under the conditions: :0.2vol.% C 3 H 8 ,2vol.％O 2 /Ar，5vol.％CO 2 Mass space velocity: 80000mL h · -1 g cat -1 )。Pt-5W/Nb 2 O 5 Catalyst propane catalytic combustion long-time reaction stability, nb 2 O 5 Carrier 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 it can be seen that CO 2 Introduction of Pt-5W/Nb 2 O 5 CatalystHas substantially no effect on the propane oxidizing activity, however, when 5vol.% H is added to the reaction gas 2 O or 5vol.% CO 2 And 5vol.% H 2 In the case of O mixture, C 3 H 8 In Pt-5W/Nb 2 O 5 The conversion on the catalyst was slightly reduced from the initial 93% to 89% stage and then remained stable for 40 hours. In addition, H is removed 2 O and CO 2 After that, C 3 H 8 Can be completely recovered. These results indicate Pt-5W/Nb 2 O 5 The catalyst has good H resistance 2 O capability.
(4) Influence of continuous high-low temperature change on catalytic activity
The temperature of Pt-5W/Nb is examined at 200-450 ℃ continuously at high and low temperatures 2 O 5 The effect of the reactivity of the catalyst propane oxidation is as follows: the temperature in the tubular heating furnace is stably maintained at 200 ℃ by a temperature control device, so that the catalyst continuously works for 10 hours at the reaction temperature. Then the reaction temperature is raised to 450 ℃ with a heating rate of 5 ℃/min. Nb (Nb) 2 O 5 Carrier 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% when the reaction temperature was 200 ℃; when the reaction temperature is rapidly increased to 450 ℃, the conversion rate of propane is immediately increased to 99.9%, and the reaction temperature can be stably maintained. The oxidation activity of the propane of the catalyst is kept unchanged after multiple heating and cooling, which shows that Pt-5W/Nb 2 O 5 The catalyst has good thermal stability.
Example 2
A Pt catalyst for catalytic combustion of propane and a preparation method thereof comprise the following steps:
Nb 2 O 5 preparation of the carrier:
niobium oxalate citric acid is dissolved in 80ml deionized water according to a proportion (the mol ratio of Nb to citric acid is 1:1 respectively), after the two are fully dissolved, the mixture is heated and stirred in a water bath at 60 ℃ until a viscous gel starts to appear, and the reactor is immediately placed in an oven at 80 DEG CDrying for 48h to obtain brown yellow solid powder, and finally roasting for 4h in air at the temperature of 700 ℃ at the temperature rising rate of 4 ℃/min at room temperature to obtain white Nb 2 O 5 And (3) powder.
Pt-xW/Nb 2 O 5 Preparation of the catalyst:
the loading of W was 5wt.% based on 1wt.% of Pt loading. Taking 1g Nb 2 O 5 The carrier was mechanically ground and pretreated by vacuum heating, and 0.01g/ml of a fresh platinum nitrate impregnation solution and 0.01g/ml of an ammonium metatungstate impregnation solution were prepared, respectively. 1ml of platinum nitrate, 5ml of ammonium metatungstate impregnating solution and Nb are respectively taken 2 O 5 Uniformly mixing the carrier, 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 at 500 ℃ for 4h (air flow rate: 100 ml/min) in a tubular heating furnace at a heating rate of 4 ℃/min to obtain the niobium oxide loaded platinum and tungsten catalyst marked as Pt-5W/Nb 2 O 5 。
The same preparation method is adopted to synthesize 0.5Pt-5W/Nb respectively 2 O 5 、1.5Pt-5W/Nb 2 O 5 And 2Pt-5W/Nb 2 O 5 Catalyst and use of the same synthetic Pt/Nb 2 O 5 As comparative example 1, 5W/Nb was synthesized 2 O 5 As comparative example 5.
The propane oxidation activity of each of the above synthetic samples was tested, and the results are shown in fig. 5: 5W/Nb 2 O 5 There was little propane oxidation activity at 350 ℃. In addition, we found that the activity of the catalyst gradually increases with increasing Pt loading, and when the Pt loading is greater than 1.5%, the propane oxidation activity of the catalyst remains substantially unchanged, so that a Pt loading of 1% is the most preferable from the viewpoint of the combined production cost and oxidation activity of the catalyst. Meanwhile, pt-5w/Nb synthesized in example 2 2 O 5 The catalyst had significantly lower propane oxidation activity than Pt-5w/Nb in example 1 2 O 5 A catalyst, which may be related to the ratio of Nb precursor to citric acid complexing agent during the support preparation. Thus, pt-5W/Nb 2 O 5 In the preparation process of the catalyst, the precursor of Nb is oxalic acidAmmonium niobium and Nb to citric acid molar ratio of 1:2 is suitable.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. A platinum catalyst for catalytic combustion of propane, characterized in that the catalyst is prepared by Nb 2 O 5 The catalyst is a carrier, pt is an active component, W is an auxiliary agent, the loading of Pt is 1-2% of the mass of the carrier, and the loading of W is 5% of the mass of the carrier;
the carrier Nb 2 O 5 The preparation method adopts a sol-gel method, and specifically comprises the following steps: respectively dissolving ammonium niobium oxalate and citric acid in deionized water according to a proportion, wherein the using molar ratio of the ammonium niobium oxalate to the citric acid is 1:2, after the two are fully dissolved, heating and stirring in a water bath at 60-100 ℃ until viscous gel starts to appear, then placing the gel in an oven at 80-140 ℃ for drying 24-48h, and finally roasting in air at 700 ℃ for 4-6 hours, wherein the heating rate is 4 ℃/min;
the catalyst is prepared by the following steps: grinding Nb 2 O 5 Pretreating the carrier by vacuum heating, preparing Pt impregnating solution and W impregnating solution, fully stirring the impregnating solution and the carrier, uniformly mixing, performing ultrasonic dispersion at room temperature for 10-20min, standing at room temperature for 12-24-h, then drying in an oven at 60-100 ℃ for 12-48-h, finally roasting at 500 ℃ for 4h in flowing air atmosphere, and heating at a temperature rate of 4 ℃ per min, wherein the product is marked as Pt-xW/Nb 2 O 5 ；
The active components and the auxiliary agents are loaded by adopting equal volume co-impregnation.
2. The platinum catalyst for catalytic combustion of propane according to claim 1, wherein the Pt loading is 1% by mass of the support and the W loading is 5% by mass of the support.
3. A method for propane as in claim 1The preparation method of the platinum catalyst for catalytic combustion is characterized by comprising the following steps: grinding Nb 2 O 5 Pretreating the carrier by vacuum heating, preparing Pt impregnating solution and W impregnating solution, fully stirring the impregnating solution and the carrier, uniformly mixing, performing ultrasonic dispersion at room temperature for 10-20min, standing at room temperature for 12-24-h, then drying in an oven at 60-100 ℃ for 12-48-h, finally roasting at 500 ℃ for 4h in flowing air atmosphere, and heating at a temperature rate of 4 ℃ per min, wherein the product is marked as Pt-xW/Nb 2 O 5 。
4. The method for preparing a platinum catalyst for propane catalytic combustion according to claim 3, wherein the Pt impregnation liquid is prepared by dissolving a soluble salt of Pt in deionized water to prepare a Pt impregnation liquid of 0.01-0.1 g/ml;
the preparation of the W dipping liquid is to dissolve soluble salt of W in deionized water to prepare 0.01-0.1g/ml of W dipping liquid.
5. Use of a platinum catalyst for catalytic combustion of propane according to claim 1, wherein the catalyst is used in low-carbon alkane exhaust gas treatment, including catalytic combustion of propane.
6. The use of a platinum catalyst for catalytic combustion of propane according to claim 5, wherein the reaction conditions for catalytic combustion of propane are: 0.2vol.% C 3 H 8， 2 vol.% O 2 Ar, alternatively, 0.2vol.% C 3 H 8， 2 vol.% O 2 Ar and 5vol.% H 2 O, mass space velocity: 80000 ml.h ∙ -1 g cat -1 。
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