CN114950422A - 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 198
- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 76
- 230000003197 catalytic effect Effects 0.000 claims abstract description 47
- 238000005470 impregnation Methods 0.000 claims abstract description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000002159 nanocrystal Substances 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- 238000011068 loading method Methods 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003345 natural gas Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 7
- 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 3
- 238000000746 purification Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 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
- 238000004873 anchoring Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 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
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 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
- 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
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000002791 soaking 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
- 238000005303 weighing Methods 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000007792 addition Methods 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010304 firing Methods 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
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052759 nickel Inorganic materials 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
- 238000009423 ventilation Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—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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- 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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- 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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- 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]
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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 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 catalytic auxiliary agent comprises any one or combination of at least two of La, Pr, Y or Nd, and the methane oxidation catalyst solves the problem of typical PdO/Al 2 O 3 Insufficient catalyst activity and long-term stability, waterPoor thermal stability; the preparation method adopts twice isometric impregnation methods to load the catalytic assistant and the Pt-doped PdO nanocrystal active component in sequence, has simple process flow, is suitable for large-scale production, and has better 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 particularly relates to a monodisperse La-anchored Pt-doped PdO nanocrystalline methane oxidation catalyst, and a preparation method and application thereof.
Background
In the face of increasingly severe air pollution problems and urgent needs for energy structure adjustment, the selection of environmentally friendly and low-carbon renewable fuels has become a necessary trend. Natural gas is the only bridge connecting traditional fossil energy and renewable energy, and becomes the most potential alternative energy due to abundant reserves, mature technology and low price. The main component of natural gas is methane. The method inevitably discharges certain concentration of methane residual gas in the utilization process of natural gas resources taking natural gas as fuel. Methane, the second major greenhouse gas, has a temperature increase potential per unit volume 21 times that of carbon dioxide, and a typical residence time in the atmosphere of 10 years. The greenhouse effect of methane on the atmosphere is therefore more severe than carbon dioxide and needs to be strictly controlled. An effective method for eliminating methane residual gas in the process of natural gas resource utilization is to oxidize methane into carbon dioxide and water by means of a catalytic oxidation technology.
CN103191733B discloses a low-concentration methane combustion catalyst and a preparation method thereof, wherein the catalyst is made of Al 2 O 3 As a carrier, the active component is selected from noble metal Pd, and the content of the noble metal Pd is calculated by elementary metal0.1 wt% -3 wt% of the total weight of the whole catalyst; the auxiliary agent comprises an auxiliary agent I and an auxiliary agent II; the first auxiliary agent is selected from one or a combination of more of noble metals of Pt, Rh, Ru and Ir, and the content of the first auxiliary agent is 0.1-20 wt% of the total weight of the active components in terms of elemental metal; the second auxiliary agent is selected from CeO 2 ，ZrO 2 ，La 2 O 3 ，TiO 2 In an amount of 1 wt% to 30 wt% of the total weight of the support, calculated as oxides. The catalyst has high content of metal oxide auxiliary agent (the total amount of the auxiliary agent II) which is 5 wt% -25 wt% of the total weight of the carrier, and three steps of dipping and loading the catalytic auxiliary agent and the active component are needed, so the catalyst has relatively high cost and complex preparation process. In addition, the catalyst had a temperature of about 550 ℃ for 90% methane conversion in the presence of water, indicating a lower activity.
CN103131488A discloses a catalyst for catalytic combustion of low-concentration methane and a preparation method thereof, wherein 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 several of platinum group noble metals Pd, Pt, Ru, Ir and Rh is used as a catalytic active component, and at least one of metal oxides of Mg, La, Fe, Mn, Ni, Co, Cr and Ca is used as the metal oxide Co-carrier. The content of the catalytic active component accounts for 0.01 to 5 percent 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 treatment or coal bed gas catalytic deoxidation treatment.
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, a liquid-phase co-reduction method is adopted to simultaneously reduce palladium acetylacetonate and gallium chloride to form PdGa bimetallic particles with uniform size, and an impregnation method is adopted to load the metal particles to Al 2 O 3 The Pd loading on the carrier was 1.0 wt%. The supported catalyst is burnt at 450 ℃ to form Pd-GaO x /Al 2 O 3 And (3) a nano catalyst. The method firstly synthesizes oleylamineThe method synthesizes the PdGa bimetallic particles and then loads the PdGa bimetallic particles, and the preparation process has the disadvantages of load, high synthesis cost and no contribution to the industrial production of the catalyst. The evaluation atmosphere of the catalyst contains no water, and the catalyst is not suitable for purifying the tail gas methane of the lean-burn natural gas vehicle with high water content.
CN104923224A discloses a supported palladium catalyst for methane combustion and a preparation method thereof, 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, and 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 catalyst adopts a heating reflux method to prepare the tin oxide carrier, and the preparation process is complex and is not beneficial to the industrial production of the catalyst. The evaluation atmosphere of the catalyst does not contain water, and the catalyst is not suitable for catalytic oxidation with methane in the tail gas of lean-burn natural gas vehicles with high water content.
In summary, how to provide a high-performance methane catalytic oxidation suitable for lean burn natural gas vehicle tail gas with high water content becomes a problem to be solved urgently at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a methane oxidation catalyst, a preparation method and application thereof, aiming at the defects of the existing catalyst, the methane oxidation catalyst effectively solves the problem of poor hydrothermal stability of the traditional palladium-based catalyst through optimized composition, and has better application prospect.
In order 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 catalytic promoter comprises any one or the 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 nanocrystals, namely PtO-PdO solid solution: the Pt doped PdO crystal phase formed by the Pt atoms which are uniform and partially replace Pd atoms in the PdO crystal lattice 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 simultaneously takes the metal in a monodisperse form rather than the metal oxide thereof as a catalytic assistant, can firmly anchor the Pt-doped PdO nanocrystal, and solves the problem of poor hydrothermal stability of the traditional palladium-based catalyst.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
In a preferred embodiment of the present invention, the content of Pd in the catalytically active component is 0.5 to 2.0 wt%, for example, 0.5 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, or 2.0 wt% based on the total mass of the methane oxidation catalyst, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In a preferred embodiment of the present invention, the content of Pt in the catalytically active component is 0.1 to 0.4 wt%, for example, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, or 0.4 wt% of the total mass of the methane oxidation catalyst, in terms of the simple substance, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In a preferred embodiment of the present invention, the promoter is contained in an amount of 1.0 to 4.0 wt%, for example, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, or 4.0 wt%, based on the total mass of the methane oxidation catalyst, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In the present 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 the catalytic auxiliary agent is weakened; too low a Pd content can significantly reduce catalyst activity.
If the Pt content is too high, the catalyst activity is inhibited; if the Pt content is too low, the water resistance and stability of the catalyst will be reduced.
If the content of the catalytic assistant is too high, the activity of the catalyst is inhibited; if the content of the promoter is too low, the stability of the catalyst may be impaired.
In a second aspect, the present invention provides a process for preparing a methane oxidation catalyst as described in the first aspect, the process comprising the steps of:
(1) loading catalytic assistant to Al by one-time isometric immersion method 2 O 3 On the carrier to obtain the catalytic assistant modified Al 2 O 3 ；
(2) Loading a catalytic active component Pt doped PdO nanocrystal to catalytic auxiliary modified Al by adopting a secondary isometric impregnation method 2 O 3 Thus obtaining Pt doped PdO-catalytic assistant/Al 2 O 3 A catalyst.
As a preferable technical scheme of the invention, the precursor salt used in the primary equal-volume impregnation method in the step (1) comprises nitrate and/or nitrate hydrate containing a catalytic promoter element.
Preferably, Al in step (1) 2 O 3 The carrier comprises gamma-Al 2 O 3 And (3) a carrier.
In the present invention, gamma-Al is exemplified 2 O 3 The carrier is obtained by firing pseudo-boehmite as a precursor.
In a preferred embodiment of the present invention, the primary equivalent-volume impregnation method in step (1) is carried out for 6 to 12 hours, for example, 6 hours, 8 hours, 10 hours, or 12 hours, but the method is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the drying temperature of the primary equivalent-volume impregnation method in step (1) is 80-120 ℃, such as 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the calcination temperature of the primary equivalent-volume impregnation method in step (1) is 750-850 ℃, such as 750 ℃, 780 ℃, 800 ℃, 820 ℃ or 850 ℃, but not limited to the recited values, and other unrecited values in the numerical range are also applicable.
Preferably, the calcination time of the primary equivalent-volume impregnation method in the step (1) is 2-5h, such as 2h, 3h, 4h or 5h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature rise rate of the calcination in the primary equivalent-volume impregnation method in the step (1) is 3-6 ℃/min, such as 3 ℃/min, 4 ℃/min, 5 ℃/min or 6 ℃/min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the precursor salt used in the secondary equivalent-volume impregnation method in the step (2) comprises nitrate and/or nitrate hydrate of palladium and nitrate and/or nitrate hydrate of Pt.
Illustratively, including but not limited to Pd (NO) 3 ) 2 ·2H 2 O and Pt (NO) 3 ) 2 Combinations of (a) and (b).
In a preferred embodiment of the present invention, the immersion time in the second isometric immersion method in step (2) is 6 to 12 hours, for example, 6 hours, 8 hours, 10 hours, or 12 hours, but the immersion time is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the drying temperature of the second equivalent-volume impregnation method in step (2) is 80-120 ℃, such as 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the roasting temperature of the secondary equivalent-volume impregnation method in the step (2) is 500-600 ℃, such as 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃ or 600 ℃, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the second equivalent-volume impregnation method in step (2) has a calcination time of 1-3h, such as 1h, 1.5h, 2h, 2.5h or 3h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the second equi-volume impregnation method in step (2) has a baking temperature rise rate of 3-6 deg.C/min, such as 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, or 6 deg.C/min, but not limited to the values listed, and other values not listed in this range are also applicable.
In a third aspect, the present invention provides the use of the methane oxidation catalyst of the first aspect for the catalytic purification of residual methane from a lean-burn natural gas vehicle exhaust.
Preferably, the water content in the lean natural gas vehicle tail gas is 5-15 vol.%, such as 5 vol.%, 7 vol.%, 9 vol.%, 11 vol.%, 13 vol.% or 15 vol.%, but is not limited to the recited values, and other non-recited values within the range of values apply equally.
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 the tail gas of the lean-burn natural gas vehicle with higher water content through the optimization of the 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 design of anchoring Pt-doped PdO nanocrystals by using the catalytic assistant in a monodisperse form greatly improves the hydrothermal stability of the prepared catalyst, so that the activity of the catalyst is unchanged after the catalyst is subjected to hydrothermal aging at 650 ℃ for 100 hours;
(2) compared with the traditional methane oxidation catalyst, the methane oxidation catalyst only takes a single Pd noble metal as an active component, and effectively improves the catalytic oxidation performance of methane by taking a Pt-doped PdO nanocrystalline structure as the active component;
(3) the preparation method of the invention adopts the 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 suitable for the tail gas of lean-burn natural gas vehicles with higher water content, and has better application prospect.
Drawings
FIG. 1 shows Pt-doped PdO-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 Pt-doped PdO-promoter/Al prepared in example 1 of the present invention 2 O 3 TEM images of the catalyst.
FIG. 3 shows the Pt doped PdO-promoter/Al prepared in example 1 of the present invention 2 O 3 Elemental profile of the catalyst.
FIG. 4 shows Pt doped PdO-promoter/Al prepared in example 1 of the present invention 2 O 3 Catalyst, its fresh state and comparative plot for methane oxidation light-off after hydrothermal aging.
FIG. 5 is a graph comparing the temperatures required to achieve 90% methane conversion in the fresh state and after hydrothermal aging for methane oxidation catalysts prepared in example 2 of the present invention and comparative examples 1-3.
FIG. 6 is a graph comparing the long cycle stability of methane oxidation catalysts prepared according to example 2 of the present invention and comparative example 2.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
In one embodiment, the present invention provides a method of preparing a methane oxidation catalyst, the method comprising the steps of:
(1) primary isometric immersion method: preparing a first precursor salt water solution by taking metal nitrate or metal nitrate hydrate as precursor salt; weighing the first precursor saline solution and soaking in gamma-Al in the same volume 2 O 3 Uniformly mixing on a carrier; sealing the immersed sample and standing for 6-12 hours at room temperature; drying the soaked sample in an oven at 80-120 ℃; then the dried sample is placed in a muffle furnace, and the temperature is raised to 750-850 ℃ at the temperature rise rate of 3-6 ℃/minRoasting for 2-5h to obtain catalytic assistant modified Al 2 O 3 ；
The metal comprises any one or the combination of at least two of La, Pr, Y and Nd;
(2) secondary isometric immersion method: with Pd (NO) 3 ) 2 ·2H 2 O and Pt (NO) 3 ) 2 Preparing a second precursor salt water solution for the precursor salt; weighing the second precursor saline solution and soaking the second precursor saline solution in the catalytic assistant modified Al in the same volume 2 O 3 Mixing uniformly; sealing the dipped sample and standing for 6-12 hours at room temperature; drying the dipped sample in an oven at 80-120 ℃; finally, the dried sample is placed in a muffle furnace, and is heated to 500-600 ℃ at the heating rate of 3-6 ℃/min for roasting for 1-3h to obtain the Pt doped PdO-catalytic assistant/Al 2 O 3 A catalyst.
The following are typical but non-limiting examples of the invention:
the embodiments 1 to 3 of the present invention each provide a method for preparing a methane oxidation catalyst, which is based on the preparation steps of the embodiment, and the specific parameter conditions are shown in table 1.
Further, specific parameters of the methane oxidation catalyst product obtained by the above-mentioned preparation method are also shown in table 1.
TABLE 1
Pt-doped PdO-catalyst promoter/Al obtained in example 1 2 O 3 The catalysts were characterized by XRD, TEM and elemental 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 refer to example 1, only difference is that only Pd is supported, Pt and La are not supported) is compared.
In addition, the fresh catalyst obtained in example 1 and the catalyst after hydrothermal aging were compared for methane oxidation light-off (test condition: 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 conversion of methane of the fresh catalyst at 450 ℃ can reach 90% under the simulated lean-burn natural gas vehicle tail gas atmosphere, and the fresh catalyst is subjected to hydrothermal aging (hydrothermal aging condition: 3.5 vol.% O) 2 、10vol.％H 2 O, 650 ℃ and 100h), the catalyst activity is unchanged.
Example 4:
this example provides a methane oxidation catalyst and a method of preparation, which is referenced to the method of preparation in example 1, except that: the concentration of the palladium salt solution was adjusted to 0.0312mol/L, thereby controlling the loading amount of Pd to 0.3 wt%.
The parameters of the obtained product were unchanged except for the loading of Pd.
Example 5:
this example provides a methane oxidation catalyst and a method of preparation, which is referenced to the method of preparation in example 2, except that: the supported amount of Pd was controlled to 2.5 wt% by adjusting the concentration of the palladium salt solution to 0.2602 mol/L.
The parameters of the obtained product were unchanged except for the loading of Pd.
Example 6:
this example provides a methane oxidation catalyst and method of preparation, which is comparable to that of example 1, except that: the concentration of the platinum salt solution was controlled to 0.05 wt% by adjusting it to 0.0028 mol/L.
The parameters of the obtained product are unchanged except for the loading amount of Pt.
Example 7:
this example provides a methane oxidation catalyst and a method of preparation, which is referenced to the method of preparation in example 2, except that: the supported amount of Pt was controlled to 0.5 wt% by adjusting the concentration of the platinum salt solution to 0.0283 mol/L.
The parameters of the obtained product were unchanged except for the Pt loading.
Example 8:
this example provides a methane oxidation catalyst and a method of preparation, which is referenced to the method of preparation in example 1, except that: the concentration of the first precursor solution was adjusted to 0.04mol/L, thereby controlling the loading amount of La to 0.5 wt%.
The parameters of the obtained product were unchanged except for the loading of La.
Example 9:
this example provides a methane oxidation catalyst and a method of preparation, which is referenced to the method of preparation in example 1, except that: the concentration of the first precursor solution was adjusted to 0.36mol/L, thereby controlling the loading of La to 4.5 wt%.
The parameters of the obtained product were unchanged except for the loading of La.
To demonstrate the influence of the contents of the components of the methane catalyst of the present invention on the catalyst performance, the stability of the catalysts obtained in examples 1-9 was determined at 450 ℃ for 100 hours, and the results were revealed 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/%) | 50h methane conversion/%) | Methane conversion at 100 h/%) | |
| 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 loading amount of Pd in example 4 was reduced, resulting in a significant decrease in catalytic activity of the catalyst; in example 5, the loading of Pd was too high, and although the initial conversion rate was high, the stability was poor and the catalytic activity decreased rapidly; in examples 6 and 7, however, the stability was deteriorated regardless of whether the amount of Pt supported was too low or too high; the loading amount of the catalytic promoter in the embodiment 8 is too low, so that the stability of the catalyst is weakened; the catalyst promoter in example 9 is supported in an excessively high amount, which not only inhibits the activity of the catalyst but also deteriorates the stability thereof.
Comparative example 1:
this example provides a process for the preparation of a methane oxidation catalyst, which is comparable to the process of example 2, except that: step (1) is not carried out, namely the catalytic promoter is not loaded, and the catalytic promoter in step (2) is modified by Al 2 O 3 Substitution to gamma-Al 2 O 3 Carrying to obtain Pt doped PdO/Al 2 O 3 A catalyst.
Comparative example 2:
this example provides a process for the preparation of a methane oxidation catalyst, which is comparable to the process of example 2, except that: no Pt is loaded in the step (2), namely only Pd (NO) 3 ) 2 ·2H 2 Preparing a second precursor salt aqueous 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 of preparing a methane oxidation catalyst, which is comparable to the method of preparation in example 2, except that: step (1) is not carried out, namely the catalyst promoter is not loaded; and Pt is not loaded in the step (2), namely only Pd (NO) 3 ) 2 ·2H 2 O is used as precursor salt to prepare a second precursor salt aqueous solution to obtain PdO/Al 2 O 3 A catalyst.
Temperature required for obtaining a methane conversion of 90% after fresh and hydrothermal aging of the methane oxidation catalyst obtained in comparative example 2 and in ratios 1 to 3 (test condition: 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: 3.5 vol.% O 2 、10vol.％H 2 O, 650 ℃ and 100 hours), 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 to the catalyst prepared by the same process without monodisperse La, thereby demonstrating the effect of monodisperse La-anchored noble metal nanocrystals on improving the hydrothermal stability of the catalyst.
Long-cycle stability of the methane oxidation catalysts obtained in comparative example 2 and comparative example 2 (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 exhibits better long-term stability compared to the Pt-free catalyst prepared by the same process, thereby reflecting the effect of the Pt-doped PdO nanocrystals on improving the long-term stability of the catalyst.
It can be seen from the above examples and comparative examples that, in the first aspect, the methane oxidation catalyst of the present invention is different from the conventional catalyst in that only a single Pd noble metal is used as an active component, and a Pt-doped PdO nanocrystalline structure is used as the active component, so that the catalytic oxidation performance and stability of methane are effectively improved, and the methane conversion rate can still reach more than 90% after 100 hours at 450 ℃; in a second aspect, aiming at the problem of poor hydrothermal stability of the traditional Pd-based catalyst, the design of anchoring Pt-doped PdO nanocrystals by using the catalytic assistant in a monodisperse form greatly improves the hydrothermal stability of the prepared catalyst, so that the activity of the catalyst is unchanged after the catalyst is subjected to hydrothermal aging at 650 ℃ for 100 hours; in the third aspect, the preparation method of the isovolumetric impregnation is adopted, the process flow is simple, and the method is suitable for large-scale production; in the fourth aspect, the methane oxidation catalyst obtained by the invention can be suitable for the tail gas of the lean-burn natural gas vehicle with higher water content, and has better application prospect.
The invention is illustrated by the above examples of products and detailed methods of the invention, but the invention is not limited to the above products and detailed methods, i.e. it is not meant that the invention must rely on the above products and detailed methods for its implementation. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents thereof, additions of additional operations, selection of specific ways, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A methane oxidation catalyst comprising Al 2 O 3 The catalyst comprises a carrier, a catalytic active component and a catalytic auxiliary agent, and is characterized in that the catalytic active component comprises Pt-doped PdO nanocrystals; the catalytic promoter comprises any one or the combination of at least two of La, Pr, Y or Nd.
2. The methane oxidation catalyst according to claim 1, wherein the catalytically active component comprises Pd in an amount of 0.5-2.0 wt.%, calculated as the elemental substance, based on the total mass of the methane oxidation catalyst.
3. A methane oxidation catalyst according to claim 1 or 2, characterized in that in said catalytically active component, Pt is present in an amount of 0.1-0.4 wt.%, calculated as the simple substance, based on the total mass of the methane oxidation catalyst.
4. A methane oxidation catalyst according to any one of claims 1 to 3, characterized in that said promoter is present in an amount of 1.0-4.0 wt.%, calculated as the element, based on the total mass of the methane oxidation catalyst.
5. A process for the preparation of a methane oxidation catalyst according to any of claims 1 to 4, comprising the steps of:
(1) loading catalytic assistant to Al by one-time isometric immersion method 2 O 3 On the carrier to obtain the catalytic assistant modified Al 2 O 3 ；
(2) Loading a catalytic active component Pt doped PdO nanocrystal to catalytic auxiliary modified Al by adopting a secondary isometric impregnation method 2 O 3 Thus obtaining Pt doped PdO-catalytic assistant/Al 2 O 3 A catalyst.
6. The preparation method according to claim 5, wherein the precursor salt used in the primary equivalent-volume impregnation method in step (1) comprises nitrate and/or nitrate hydrate containing a catalyst promoter element;
preferably, Al in step (1) 2 O 3 The carrier comprises gamma-Al 2 O 3 And (3) a carrier.
7. The method according to claim 5 or 6, wherein the primary equivalent-volume impregnation method in step (1) is carried out for 6-12 h;
preferably, the drying temperature of the primary equal-volume impregnation method in the step (1) is 80-120 ℃;
preferably, the roasting temperature of the primary equal-volume impregnation method in the step (1) is 750-850 ℃;
preferably, the roasting time of the primary equivalent-volume impregnation method in the step (1) is 2-5 h;
preferably, the roasting temperature rise rate of the primary equal-volume impregnation method in the step (1) is 3-6 ℃/min.
8. The method for preparing according to any one of claims 5 to 7, wherein the precursor salts used in the second equivalent-volume impregnation method in step (2) include nitrate and/or nitrate hydrate of palladium and nitrate and/or nitrate hydrate of Pt.
9. The method according to any one of claims 5 to 8, wherein the second isovolumetric impregnation in step (2) is carried out for a period of 6 to 12 hours;
preferably, the drying temperature of the secondary equivalent-volume impregnation method in the step (2) is 80-120 ℃;
preferably, the roasting temperature of the secondary equal-volume impregnation method in the step (2) is 500-600 ℃;
preferably, the roasting time of the secondary equivalent-volume impregnation method in the step (2) is 1-3 h;
preferably, the roasting temperature rise rate of the secondary equivalent-volume impregnation method in the step (2) is 3-6 ℃/min.
10. Use of a methane oxidation catalyst according to any one of claims 1 to 3, wherein the methane oxidation catalyst is used for catalytic purification of residual methane in the tail gas of a lean-burn natural gas vehicle;
preferably, the water content in the lean burn natural gas vehicle tail gas is 5-15 vol.%.
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