CN114950422B - Methane oxidation catalyst and preparation method and application thereof - Google Patents
Methane oxidation catalyst and preparation method and application thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 230000003647 oxidation Effects 0.000 title claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 78
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- 238000005470 impregnation Methods 0.000 claims abstract description 33
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 239000003345 natural gas Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001802 infusion Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910002676 Pd(NO3)2·2H2O Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/018—Natural gas engines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Chemical & Material Sciences (AREA)
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- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a methane oxidation catalyst, a preparation method and application thereof, wherein the methane oxidation catalyst comprises Al 2 O 3 Support, catalytically active component comprising Pt-doped P, and catalytic promoterdO nanocrystalline, the catalyst auxiliary agent comprises any one or a combination of at least two of La, pr, Y or Nd, and the methane oxidation catalyst solves the typical PdO/Al 2 O 3 The catalyst has insufficient activity and poor long-period stability and hydrothermal stability; the preparation method sequentially loads the catalytic auxiliary agent and the Pt doped PdO nanocrystalline active component by adopting a twice isovolumetric impregnation method, has simple process flow, is suitable for large-scale production, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, relates to a methane oxidation catalyst and a preparation method and application thereof, and in particular relates to a monodisperse La anchored Pt doped PdO nanocrystalline methane oxidation catalyst and a preparation method and application thereof.
Background
In face of the increasingly severe problems of air pollution and urgent demands for energy structure adjustment, the selection of environmentally friendly, low-carbon renewable fuels has become a necessary trend. Natural gas is used as the only bridge for connecting traditional fossil energy and renewable energy, and is the most potential alternative energy due to abundant reserves, mature technology and low price. The main component of natural gas is methane. A certain concentration of methane residual gas is inevitably discharged in the natural gas resource utilization process using natural gas as fuel. Methane is used as the second major greenhouse gas, and its heating potential per unit volume is 21 times that of carbon dioxide, and the residence time in the atmosphere is typically 10 years. The greenhouse effect of methane on the atmosphere is therefore more severe than that of carbon dioxide, requiring strict control. An effective method for eliminating methane residual gas in the natural gas resource utilization process is to oxidize methane into carbon dioxide and water by means of catalytic oxidation technology.
CN103191733B discloses a low-concentration methane combustion catalyst and a preparation method thereof, the catalyst uses Al 2 O 3 As a carrier, the active component is selected from noble metal Pd, and the content of the active component is 0.1-3 wt% of the total weight of the whole catalyst based on the single metal; the auxiliary agent comprises an auxiliary agent I and an auxiliary agent II; the auxiliary agent I is one or a combination of more than one noble metal Pt, rh, ru, ir, and the content of the auxiliary agent I is 0.1-20 wt% of the total weight of the active components based on the single metal; the auxiliary agent II is selected from CeO 2 ，ZrO 2 ，La 2 O 3 ，TiO 2 One or a combination of the above materials, the content of which is 1 to 30 weight percent of the total weight of the carrier based on oxide. The catalyst has high metal oxide additive (additive II total amount) content which is 5-25 wt% of the total weight of the carrier, and three steps of impregnation are needed to load the catalyst additive and the active components, so the catalyst has relatively high cost and complex preparation process. In addition, the catalyst had a temperature of about 550 ℃ up to 90% methane conversion under aqueous conditions, indicating a relatively low activity.
CN103131488A discloses a catalyst for catalytic combustion of low concentration methane and a preparation method thereof, the catalyst comprises a catalytic active component and a catalyst carrier Al 2 O 3 And a metal oxide co-carrier, wherein one or a combination of a plurality of platinum noble metals Pd, pt, ru, ir, rh is used as a catalytic active component, and at least one of Mg, la, fe, mn, ni, co, cr, ca metal oxides is used as the metal oxide co-carrier. The content of the catalytic active component accounts for 0.01-5% of the total mass of the catalyst; the metal oxide co-carrier accounts for 5-45% of the total mass of the catalyst. The catalyst is applied to a methane catalytic combustion process or other hydrocarbon catalytic removal processes aiming at mine ventilation gas control or coal bed gas catalytic deoxidation control.
CN106693987A discloses a palladium gallium oxide bimetallic nano-catalyst for efficiently catalyzing methane combustion and a preparation method thereof, wherein the preparation method comprises the following steps: in an oleylamine system, palladium acetylacetonate and gallium chloride are simultaneously reduced by adopting a liquid phase co-reduction method to form PdGa bimetallic particles with uniform size, and then the metal particles are loaded on Al by adopting an impregnation method 2 O 3 The Pd loading on the support was 1.0wt%. Burning the supported catalyst at 450 deg.c to form Pd-GaO x /Al 2 O 3 A nano catalyst. According to the method, the PdGa bimetallic particles are synthesized by an oleylamine synthesis method and then loaded, and the preparation process is loaded, so that the synthesis cost is high, and the industrial production of the catalyst is not facilitated. The catalyst is free from water in the evaluation atmosphere, and is not suitable for purifying methane in the tail gas of a lean-burn natural gas vehicle with high water content.
CN104923224a discloses a supported palladium catalyst for methane combustion and a preparation method, the catalyst is characterized in that an active component is noble metal palladium, an auxiliary agent is rare earth oxide, alkali metal or alkaline earth metal oxide, a carrier is tin oxide, wherein the content of palladium is 0.1-5%, the content of rare earth oxide is 3-10%, and the content of alkali metal or alkaline earth metal oxide is 0.01-2%. The tin oxide carrier is prepared by adopting a heating reflux method, and the preparation process is complex, so that the catalyst is not beneficial to the industrial production of the catalyst. The catalyst is free from water in the evaluation atmosphere, and is not suitable for the catalytic oxidation of methane in the tail gas of the lean-burn natural gas vehicle with high water content.
In summary, how to provide a method for catalytic oxidation of high-performance methane in lean-burn natural gas vehicle exhaust with high water content is a current urgent problem to be solved.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a methane oxidation catalyst, a preparation method and application thereof, and the methane oxidation catalyst effectively solves the problem of poor hydrothermal stability of the traditional palladium-based catalyst by optimizing the composition aiming at the defects existing in the existing catalyst, and has a good application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a methane oxidation catalyst comprising Al 2 O 3 The catalyst comprises a carrier, a catalytic active component and a catalytic auxiliary agent, wherein the catalytic active component comprises Pt doped PdO nanocrystalline; the catalyst promoter comprises any one or a combination of at least two of La, pr, Y or Nd.
In the invention, on one hand, the methane oxidation catalyst utilizes Pt doped PdO nanocrystalline, namely PtO-PdO solid solution: the Pt doped PdO crystalline phase formed by partially replacing Pd atoms in the PdO crystal lattice with uniform Pt atoms is used as an active component, and the controllable synthesis of the active component can effectively solve the problems of insufficient water resistance and long-period stability of the PdO active phase; on the other hand, the methane oxidation catalyst takes the metal in a monodispersed form instead of the metal oxide as a catalytic auxiliary agent, so that Pt doped PdO nanocrystalline can be firmly anchored, and the problem of poor hydrothermal stability of the traditional palladium-based catalyst is solved.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred embodiment of the present invention, pd is contained in the catalytically active component in an amount of 0.5 to 2.0wt%, for example, 0.5wt%, 0.8wt%, 1.0wt%, 1.2wt%, 1.5wt%, 1.8wt% or 2.0wt%, etc., based on the total mass of the methane oxidation catalyst, based on the simple substance, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the content of Pt in the catalytically active component is 0.1 to 0.4wt%, for example, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt% or 0.4wt%, etc., based on the total mass of the methane oxidation catalyst, based on the simple substance, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the catalyst auxiliary is contained in an amount of 1.0 to 4.0wt%, for example, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt% or 4.0wt% based on the total mass of the methane oxidation catalyst, based on the simple substance, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
In the invention, the content of each component of the methane oxidation catalyst has an important influence on the performance. If the Pd content is too high, the intrinsic activity of the catalyst is reduced, and the modification effect of Pt and a catalytic auxiliary agent is weakened; too low a Pd content may significantly reduce the catalyst activity.
If the Pt content is too high, the catalyst activity is inhibited; too low Pt content reduces the water resistance and stability of the catalyst.
If the content of the catalyst auxiliary agent is too high, the activity of the catalyst is inhibited; too low a catalyst promoter content may impair catalyst stability.
In a second aspect, the present invention provides a method for preparing the methane oxidation catalyst according to the first aspect, the method comprising the steps of:
(1) The catalytic auxiliary agent is loaded on Al by adopting a once isovolumetric impregnation method 2 O 3 On the carrier, the catalyst auxiliary agent modified Al is obtained 2 O 3 ；
(2) The catalytic active component Pt doped PdO nanocrystalline is loaded to the catalytic auxiliary agent modified Al by adopting a secondary isovolumetric impregnation method 2 O 3 On the surface, pt doped PdO-catalyst auxiliary agent/Al is obtained 2 O 3 A catalyst.
As a preferred embodiment of the present invention, the precursor salt used in the one-time isovolumetric impregnation method in step (1) includes nitrate and/or nitrate hydrate containing a catalyst auxiliary element.
Preferably, the Al of step (1) 2 O 3 The carrier comprises gamma-Al 2 O 3 A carrier.
In the present invention, illustratively, gamma-Al 2 O 3 The carrier is prepared by firing pseudo-boehmite serving as a precursor.
In a preferred embodiment of the present invention, the one-time isovolumetric impregnation method in step (1) has an impregnation time of 6 to 12 hours, for example, 6 hours, 8 hours, 10 hours or 12 hours, etc., but the present invention is not limited to the listed values, and other values not listed in the range of values are equally applicable.
Preferably, the drying temperature of the primary isovolumetric infusion method in step (1) is 80-120 ℃, such as 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the baking temperature of the primary isovolumetric infusion method in step (1) is 750-850 ℃, such as 750 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃ or 850 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the calcination time of the one-time isovolumetric impregnation method in step (1) is 2 to 5 hours, for example, 2 hours, 3 hours, 4 hours or 5 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the baking temperature rise rate of the one-time isovolumetric infusion method in the step (1) is 3-6 ℃/min, such as 3 ℃/min, 4 ℃/min, 5 ℃/min or 6 ℃/min, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the precursor salt used in the second isovolumetric impregnation method in step (2) includes a nitrate and/or nitrate hydrate of palladium, and a nitrate and/or nitrate hydrate of Pt.
Exemplary include, but are not limited to Pd (NO 3 ) 2 ·2H 2 O and Pt (NO) 3 ) 2 Is a combination of (a) and (b).
In a preferred embodiment of the present invention, the impregnation time of the secondary isovolumetric impregnation method in the step (2) is 6 to 12 hours, for example, 6 hours, 8 hours, 10 hours or 12 hours, etc., but the present invention is not limited to the listed values, and other non-listed values within the range of the values are equally applicable.
Preferably, the drying temperature of the secondary isovolumetric infusion method in step (2) is 80-120 ℃, such as 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the baking temperature of the secondary isovolumetric infusion method in step (2) is 500-600 ℃, for example 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the roasting time of the secondary isovolumetric impregnation method in the step (2) is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours, etc., but the method is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Preferably, the baking temperature rise rate of the secondary isovolumetric infusion method in the step (2) is 3-6 ℃/min, such as 3 ℃/min, 4 ℃/min, 5 ℃/min or 6 ℃/min, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a third aspect, the present invention provides the use of a methane oxidation catalyst according to the first aspect for the catalytic purification of residual methane in lean-burn natural gas vehicle exhaust.
Preferably, the water content in the lean natural gas vehicle exhaust is 5-15vol.%, e.g., 5vol.%, 7vol.%, 9vol.%, 11vol.%, 13vol.%, or 15vol.%, etc., but is not limited to the recited values, other non-recited values within the range of values are equally applicable.
The high-concentration water content can greatly inhibit the methane oxidation activity of the catalyst, and the methane oxidation catalyst obtained by the invention can be suitable for lean-burn natural gas vehicle tail gas with higher water content through optimization of structural components, and has better application prospect.
Compared with the prior art, the invention has the following beneficial effects:
(1) Aiming at the problem of poor hydrothermal stability of the traditional Pd-based catalyst, the methane oxidation catalyst greatly improves the hydrothermal stability of the prepared catalyst by adopting the design of anchoring Pt doped PdO nanocrystalline by adopting a catalyst auxiliary agent in a monodispersed form, so that the catalyst activity is unchanged after the catalyst is subjected to hydrothermal aging for 100 hours at 650 ℃;
(2) Compared with the traditional catalyst, the catalyst provided by the invention has the advantages that only a single Pd noble metal is used as an active component, and the Pt doped PdO nanocrystalline structure is used as the active component, so that the methane catalytic oxidation performance is effectively improved;
(3) The invention adopts the preparation method of equal volume impregnation, has simple process flow and is suitable for large-scale production;
(4) The methane oxidation catalyst obtained by the invention can be applied to the tail gas of the lean-burn natural gas vehicle with higher water content, and has better application prospect.
Drawings
FIG. 1 shows a Pt-doped PdO-catalyst promoter/Al prepared in example 1 of the present invention 2 O 3 Catalyst and existing PdO/Al 2 O 3 XRD contrast pattern of the catalyst.
FIG. 2 shows a Pt-doped PdO-catalyst promoter/Al prepared in example 1 of the present invention 2 O 3 TEM image of the catalyst.
FIG. 3 shows a Pt-doped PdO-catalyst promoter/Al prepared in example 1 of the present invention 2 O 3 Element profile of the catalyst.
FIG. 4 shows a Pt-doped PdO-catalyst promoter/Al prepared in example 1 of the present invention 2 O 3 A comparison of the fresh state of the catalyst and the oxidation and ignition of methane after hydrothermal aging.
FIG. 5 is a graph comparing the temperatures required to achieve 90% methane conversion after fresh and hydrothermal aging of the methane oxidation catalysts prepared in example 2 and comparative examples 1-3 of the present invention.
FIG. 6 is a graph comparing the long-period stability of the methane oxidation catalysts prepared in example 2 and comparative example 2 of the present invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
In one embodiment, the present invention provides a method for preparing a methane oxidation catalyst, the method comprising the steps of:
(1) Primary isovolumetric impregnation: preparing a first precursor salt aqueous solution by taking metal nitrate or metal nitrate hydrate as precursor salt; measuring the first precursor salt water solution to dip in gamma-Al in equal volume 2 O 3 On the carrier, mixing uniformly; sealing the immersed sample and standing at room temperature for 6-12 hours; placing the immersed sample in an oven at 80-120 ℃ for drying; then placing the dried sample in a muffle furnace, heating to 750-850 ℃ at a heating rate of 3-6 ℃/min, and roasting for 2-5h to obtain the catalytic auxiliary agent modified Al 2 O 3 ；
The metal comprises any one or a combination of at least two of La, pr, Y, nd;
(2) Secondary isovolumetric impregnation: with Pd (NO) 3 ) 2 ·2H 2 O and Pt (NO) 3 ) 2 Preparing a second precursor salt water solution for precursor salt; measuring the second precursor saline solution to dip the catalyst promoter modified Al in an equal volume 2 O 3 Uniformly mixing; sealing the immersed sample and standing at room temperature for 6-12 hours; placing the immersed sample in an oven at 80-120 ℃ for drying; finally, placing the dried sample in a muffle furnace, heating to 500-600 ℃ at a heating rate of 3-6 ℃/min, and roasting for 1-3h to obtain the Pt doped PdO-catalyst auxiliary agent/Al 2 O 3 A catalyst.
The following are exemplary but non-limiting examples of the invention:
examples 1 to 3 of the present invention each provide a method for producing a methane oxidation catalyst based on the production steps of the detailed description section, with specific parameter conditions shown in table 1.
In addition, specific parameters of the methane oxidation catalyst product obtained by the above preparation method are also shown in table 1.
TABLE 1
For the product obtained in example 1Pt doped PdO-catalyst promoter/Al 2 O 3 The catalysts were characterized by XRD, TEM and element distribution, respectively, and the results are shown in FIGS. 1-3, respectively. Wherein FIG. 1 is also related to the existing PdO/Al 2 O 3 The catalyst (preparation method referred to example 1, only difference is that Pd alone, pt and La are not supported) was compared.
In addition, the fresh catalyst obtained in example 1 and the methane oxidation initiation of the catalyst after hydrothermal aging (test conditions: 1000ppm CH 4 ，3.5vol.％O 2 ，6vol.％CO 2 ，2000ppm CO，1000ppm NO，10vol.％H 2 O，300000mL·g cat. -1 ·h -1 WHSV), the results are shown in fig. 4. As can be seen from FIG. 4, the methane conversion of the fresh catalyst at 450 ℃ under the simulated lean-burn natural gas vehicle exhaust atmosphere can reach 90 percent, and after hydrothermal aging (hydrothermal aging condition: 3.5vol.% O 2 、10vol.％H 2 O, 650 ℃, 100 h), the catalyst activity is unchanged.
Example 4:
this example provides a methane oxidation catalyst and a method of preparation, which differs from the method of preparation in example 1 only in that: the Pd loading was controlled to 0.3wt% by adjusting the concentration of the palladium salt solution to 0.0312 mol/L.
The parameters of the obtained product are unchanged except Pd loading.
Example 5:
this example provides a methane oxidation catalyst and a method of preparation, which differs from the method of preparation in example 2 only in that: the Pd loading was controlled to 2.5wt% by adjusting the concentration of the palladium salt solution to 0.2602 mol/L.
The parameters of the obtained product are unchanged except Pd loading.
Example 6:
this example provides a methane oxidation catalyst and a method of preparation, which differs from the method of preparation in example 1 only in that: the concentration of the platinum salt solution was adjusted to 0.0028mol/L, thereby controlling the concentration to 0.05wt%.
The parameters of the obtained product are unchanged except the loading amount of Pt.
Example 7:
this example provides a methane oxidation catalyst and a method of preparation, which differs from the method of preparation in example 2 only in that: the Pt loading was controlled to 0.5wt% by adjusting the concentration of the platinum salt solution to 0.0283 mol/L.
The parameters of the obtained product are unchanged except the loading amount of Pt.
Example 8:
this example provides a methane oxidation catalyst and a method of preparation, which differs from the method of preparation in example 1 only in that: the La loading was controlled to 0.5wt% by adjusting the concentration of the first precursor solution to 0.04 mol/L.
The parameters of the obtained product are unchanged except the load of La.
Example 9:
this example provides a methane oxidation catalyst and a method of preparation, which differs from the method of preparation in example 1 only in that: the La loading was controlled to 4.5wt% by adjusting the concentration of the first precursor solution to 0.36 mol/L.
The parameters of the obtained product are unchanged except the load of La.
To demonstrate the effect of the content of the components of the methane catalysts of the invention on the catalyst performance, the stability of the catalysts obtained in examples 1 to 9 was determined at 450℃for 100 hours, as reflected by the change in methane conversion (test conditions: 1000ppm CH 4 ，3.5vol.％O 2 ，6vol.％CO 2 ，2000ppm CO，1000ppm NO，10vol.％H 2 O，300000mL·g cat. -1 ·h -1 WHSV), the results are shown in table 2.
TABLE 2
| Initial methane conversion/% | Methane conversion/% | Methane conversion/% | |
| Example 1 | 90 | 90 | 90 |
| Example 2 | 98 | 98 | 98 |
| Example 3 | 92 | 92 | 92 |
| Example 4 | 35 | 31 | 30 |
| Example 5 | 99 | 85 | 78 |
| Example 6 | 88 | 75 | 65 |
| Example 7 | 95 | 90 | 85 |
| Example 8 | 90 | 86 | 84 |
| Example 9 | 78 | 75 | 73 |
As can be seen from Table 2, the methane oxidation catalyst obtained by the invention has high methane conversion rate and good stability; the reduction in the loading of Pd in example 4 resulted in a significant reduction in the catalytic activity of the catalyst; in example 5, the Pd loading is too high, and the initial conversion rate is higher, but the stability is poor, and the catalyst performance is rapidly reduced; in examples 6 and 7, however, too low or too high a Pt loading resulted in poor stability; the catalyst promoter loading in example 8 is too low, impairing the stability of the catalyst; too high a loading of the catalyst promoter in example 9 not only inhibits the activity of the catalyst, but also reduces its stability.
Comparative example 1:
this example provides a method for preparing a methane oxidation catalyst, which is different from the preparation method in example 2 only in that: step (1) is not carried out, namely no catalyst auxiliary agent is loaded, and the catalyst auxiliary agent in step (2) is modified into Al 2 O 3 Replaced by gamma-Al 2 O 3 A carrier, and Pt doped PdO/Al is obtained 2 O 3 A catalyst.
Comparative example 2:
this example provides a method for preparing a methane oxidation catalyst, which is different from the preparation method in example 2 only in that: in step (2), NO Pt is supported, i.e. Pd (NO) 3 ) 2 ·2H 2 Preparing a second precursor salt water solution by taking O as precursor salt to obtain PdO-La/Al 2 O 3 A catalyst.
Comparative example 3:
this example provides a method for preparing a methane oxidation catalyst, which refers to the preparation method in example 2, with the difference that: step (1) is not carried out, namely, no catalytic auxiliary agent is loaded; and in step (2) NO Pt is supported, i.e. Pd (NO) 3 ) 2 ·2H 2 Preparing a second precursor salt water solution by taking O as precursor salt to obtain PdO/Al 2 O 3 A catalyst.
Comparative example 2 and methane oxidation catalysts obtained in examples 1-3, the temperature required to achieve a methane conversion of 90% after fresh and hydrothermal aging (test conditions: 1000ppm CH) 4 ，3.5vol.％O 2 ，6vol.％CO 2 ，2000ppm CO，1000ppm NO，10vol.％H 2 O，300000mL·g cat. -1 ·h -1 WHSV; hydrothermal aging conditions: 3.5vol.% O 2 、10vol.％H 2 O, 650 ℃, 100 h), and the results are shown in FIG. 5. As can be seen from fig. 5, the catalyst containing monodisperse La has less activity loss after hydrothermal aging compared with the catalyst prepared by the same process and does not contain monodisperse La, thereby exhibiting the effect of the monodisperse La anchored noble metal nanocrystal on improving the hydrothermal stability of the catalyst.
Comparative example 2 and comparative example 2 Long period stability of the methane oxidation catalyst obtained (test conditions: 1000ppm CH 4 ，3.5vol.％O 2 ，6vol.％CO 2 ，2000ppm CO，1000ppm NO，10vol.％H 2 O，300000mL·g cat. -1 ·h -1 WHSV), the results are shown in fig. 6. As can be seen from FIG. 6, the Pt-containing catalyst showed a higher level than the Pt-free catalyst prepared by the same processGood long-period stability, thereby showing the effect of Pt doped PdO nanocrystalline on improving the long-period stability of the catalyst.
In summary, the above examples and comparative examples show that, in the first aspect, compared with the traditional methane oxidation catalyst, only a single Pd noble metal is used as an active component, and by adopting a Pt doped PdO nanocrystalline structure as an active component, the methane catalytic oxidation performance and stability are effectively improved, and the methane conversion rate can still reach more than 90% after 100 hours at 450 ℃; in the second aspect, aiming at the problem of poor hydrothermal stability of the traditional Pd-based catalyst, the methane oxidation catalyst greatly improves the hydrothermal stability of the prepared catalyst by adopting a monodisperse catalytic auxiliary agent anchored Pt doped PdO nanocrystalline design, so that the catalyst has unchanged activity after being subjected to 650 ℃ hydrothermal aging for 100 hours; in the third aspect, the invention adopts a preparation method of isovolumetric impregnation, has simple process flow and is suitable for large-scale production; in the fourth aspect, the methane oxidation catalyst obtained by the invention can be applied to the lean-burn natural gas vehicle tail gas with higher water content, and has better application prospect.
The present invention is illustrated by the above examples as products and detailed methods, but the present invention is not limited to the above products and detailed methods, i.e., it is not meant that the present invention must be practiced with the above products and detailed methods. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for operation of the present invention, addition of auxiliary operations, selection of specific modes, etc., are intended to fall within the scope of the present invention and the scope of the disclosure.
Claims (14)
1. A method for preparing a methane oxidation catalyst, comprising the steps of:
(1) The catalytic auxiliary agent is loaded on Al by adopting a once isovolumetric impregnation method 2 O 3 On the carrier, the catalyst auxiliary agent modified Al is obtained 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The roasting temperature of the primary isovolumetric impregnation method is 750-850 ℃;
(2) The catalytic active component Pt doped PdO nanocrystalline is loaded by adopting a secondary isovolumetric impregnation methodTo catalytic auxiliary agent modified Al 2 O 3 On the surface, pt doped PdO-catalyst auxiliary agent/Al is obtained 2 O 3 A catalyst; the roasting temperature of the secondary isovolumetric impregnation method is 500-600 ℃;
the methane oxidation catalyst comprises Al 2 O 3 The catalyst comprises a carrier, a catalytic active component and a catalytic auxiliary agent, wherein the catalytic active component comprises Pt doped PdO nanocrystalline; the catalyst auxiliary agent comprises any one or a combination of at least two of La, pr, Y or Nd;
the content of the catalytic auxiliary agent is 1.0-4.0wt% of the total mass of the methane oxidation catalyst based on the simple substance;
in the catalytic active component, pd accounts for 0.8-2.0wt% of the total mass of the methane oxidation catalyst in terms of simple substance;
in the catalytic active component, pt is calculated as a simple substance, and the content of the Pt accounts for 0.1-0.4wt% of the total mass of the methane oxidation catalyst.
2. The method of claim 1, wherein the precursor salt used in the one-time isovolumetric impregnation method of step (1) comprises nitrate and/or nitrate hydrate containing a catalytic promoter element.
3. The method according to claim 1, wherein the Al in the step (1) 2 O 3 The carrier comprises gamma-Al 2 O 3 A carrier.
4. The method according to claim 1, wherein the one-time isovolumetric impregnation method of step (1) has an impregnation time of 6 to 12 hours.
5. The method according to claim 1, wherein the primary isovolumetric impregnation method in step (1) is carried out at a drying temperature of 80 to 120 ℃.
6. The method according to claim 1, wherein the one-time isovolumetric impregnation method of step (1) has a calcination time of 2 to 5 hours.
7. The method according to claim 1, wherein the one-time isovolumetric impregnation method in step (1) has a firing temperature increase rate of 3 to 6 ℃/min.
8. The method of claim 1, wherein the precursor salt used in the second isovolumetric impregnation method of step (2) comprises a nitrate and/or nitrate hydrate of palladium and a nitrate and/or nitrate hydrate of Pt.
9. The method according to claim 1, wherein the impregnation time of the secondary isovolumetric impregnation method in step (2) is 6 to 12 hours.
10. The method according to claim 1, wherein the drying temperature of the secondary isovolumetric impregnation method in step (2) is 80 to 120 ℃.
11. The method according to claim 1, wherein the firing time of the secondary isovolumetric impregnation method in step (2) is 1 to 3 hours.
12. The method according to claim 1, wherein the firing temperature rise rate of the secondary isovolumetric impregnation method in step (2) is 3 to 6 ℃/min.
13. Use of a methane oxidation catalyst according to any of claims 1-12, for the catalytic purification of residual methane in lean-burn natural gas vehicle exhaust.
14. The use according to claim 13, wherein the lean-burn natural gas vehicle exhaust has a water content of 5-15vol.%.
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