CN113813951A - Mesoporous catalyst and preparation method and application thereof - Google Patents
Mesoporous catalyst and preparation method and application thereof Download PDFInfo
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- CN113813951A CN113813951A CN202010569005.1A CN202010569005A CN113813951A CN 113813951 A CN113813951 A CN 113813951A CN 202010569005 A CN202010569005 A CN 202010569005A CN 113813951 A CN113813951 A CN 113813951A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 41
- 239000010703 silicon Substances 0.000 claims abstract description 41
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 7
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 7
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 122
- 239000002243 precursor Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 42
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- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 17
- 239000012265 solid product Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
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- 239000012691 Cu precursor Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002736 nonionic surfactant Substances 0.000 claims description 2
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- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- 238000005691 oxidative coupling reaction Methods 0.000 description 13
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- 238000005516 engineering process Methods 0.000 description 8
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 8
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- 239000000047 product Substances 0.000 description 8
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- 229910052799 carbon Inorganic materials 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000005481 NMR spectroscopy Methods 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 229910052712 strontium Inorganic materials 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/638—Pore volume more than 1.0 ml/g
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to the field of catalysis, and discloses a mesoporous catalyst, and a preparation method and application thereof. The catalyst comprises a silicon-containing carrier and an active component, wherein at least part of the active component is embedded into a framework of the silicon-containing carrier, and the active component comprises at least one of La, Ce, Pm, Sm, Gd, Tb, Tm, Lu, Sc, Y, Ag, Pt, Cu and Ti; wherein the molar ratio of the active component calculated by the metal element to the silicon-containing carrier calculated by Si is 0.01-0.5: 1. at least part of the active component of the mesoporous catalyst is embedded into the framework of the carrier, so that the active sites of the active component are increased.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a mesoporous catalyst and a preparation method and application thereof.
Background
The technology for preparing ethylene from natural gas comprises two routes of indirect conversion and direct conversion. The indirect conversion comprises the technology of preparing ethylene from natural gas by Methanol (MTO), the technology of preparing ethylene by a Fischer-Tropsch synthesis route (FTO) and the like; the direct conversion comprises methane anaerobic dehydrogenation technology (MDA), methane oxidative coupling ethylene preparation technology (OCM) and the like. The indirect methane conversion process is complex, and the methane needs to be converted into synthesis gas at high temperature, and then the synthesis gas is subjected to one-step or two-step method to synthesize the ethylene. From the energy point of view, the indirect conversion needs to completely break the C-H bonds which should be partially remained in the product to generate synthesis gas, and then the synthesis gas is recombined under the action of a catalyst to obtain the hydrocarbon product, which is non-atomic economical and causes energy waste. Ethylene and other hydrocarbon products above C2 can also be produced from methane by the Oxidative Coupling (OCM) reaction of methane. The technology is reducing ethylene (C)2H4) The method has great potential in the aspects of cost, energy and environmental emission in production, and meanwhile, because the methane oxidative coupling reaction is a strong exothermic reaction and is carried out at high temperature and is limited by the reaction temperature and the technical difficulty of the reaction process, no industrial scale production is produced so far, so that the development of the methane oxidative coupling catalyst with excellent performance has practical significance.
The direct conversion of methane has been regarded by the industry and scholars because of the simple process, wherein the anaerobic dehydrogenation technique is difficult to activate methane, the reaction usually requires a high temperature above 1000 ℃, and the products are mainly aromatic hydrocarbons and a small amount of C2 and above; the reaction temperature for preparing ethylene by Oxidative Coupling (OCM) is low, the important industrial raw material ethylene is taken as a main product, the industrial prospect is wide, and the method is always in a generally good technical route. However, the performance of the catalyst has a large gap from the industrial demand, and although the research has been conducted for decades, the catalyst technology has not been a major breakthrough, so that the high-performance catalyst is a core problem of whether the OCM technology can be industrially applied. In recent decades, with the continuous appearance of characterization means and novel materials, some progress has been made in catalyst composition (formula) and preparation method, but in general, the reaction process still needs to be carried out at a higher temperature to obtain a higher methane conversion rate. It is known that high temperature easily causes deep oxidation of methane and C2 and above hydrocarbons to generate carbon monoxide and carbon dioxide, which causes selectivity reduction of C2 and above hydrocarbons, and affects yield of target products; meanwhile, a series of problems such as loss of active components, sintering, carbon deposition and the like are caused by high temperature, and the service life of the catalyst is influenced. Therefore, researchers have been working to find low temperature high efficiency methane oxidative coupling catalysts that can achieve high yield while extending the useful life of the catalyst.
In order to reduce the reaction temperature of the methane oxidative coupling catalyst, researchers have done much work, such as CN101385982A, a mesoporous molecular sieve catalyst for preparing ethylene by methane oxidative coupling and a preparation method thereof, in which a mesoporous molecular sieve (mesoporous molecular sieve SBA-15) is used as a catalyst carrier for modification, and Na is added2WO4And Mn or Na2WO4And Mn, M (M ═ Li, Ce, Zr, La or Sr) and other catalytic active components are assembled into the pores of the mesoporous molecular sieve, so that the catalytic active components are highly isolated and dispersed, and the activity and stability of the catalyst are improved. The catalyst is prepared by adopting mixed oxide calcined at high temperature (950 ℃), CN109922880A is a methane Oxidative Coupling (OCM) catalyst composition, and is characterized by the general formula Sr1.0CeaYbbOcWherein a is from about 0.01 to about 2.0, wherein b is from about 0.01 to about 2.0, wherein the sum (a + b) is not 1.0, and wherein c balances the oxidation state. CN109890501A an Oxidative Coupling of Methane (OCM) catalyst composition comprising: (i) Sr-Ce-Yb-O perovskite; (ii) one or more metal oxides selected from the group consisting of strontium (Sr), cerium (Ce) and ytterbium (Yb); wherein the one or more oxides comprise: a single metal oxide, a mixture of single metal oxides, a mixed metal oxide, a mixture of mixed metal oxides, a mixture of single and mixed metal oxides, or a combination thereof. The prepared catalyst has the problems of high reaction temperature, complex catalyst preparation process and long preparation period, and brings difficulty to industrial scale-up production.
Disclosure of Invention
The invention aims to solve the problems of low reaction activity, short service life and long preparation period of the catalyst in the prior art, and provides a mesoporous catalyst, a preparation method and application thereof, wherein at least part of active components of the mesoporous catalyst are embedded into a framework of a carrier, so that the active sites of the active components are increased; when the mesoporous catalyst is prepared, the mesoporous material template is mixed with the precursor of the active component, so that the active component can enter the framework of the carrier, and the catalyst has more active sites; and the mesoporous catalyst can enable the reaction for preparing the carbon dioxide and the hydrocarbon from the methane to be carried out at a lower temperature (such as within the range of 450-750 ℃), reduces the requirements on a reactor and operating conditions, has higher methane conversion rate and higher selectivity of the carbon dioxide and the hydrocarbon, and is more beneficial to industrial scale-up production.
In order to achieve the above object, a first aspect of the present invention provides a mesoporous catalyst comprising a silicon-containing carrier and an active component, wherein at least a portion of the active component is embedded in a framework of the silicon-containing carrier, and the active component comprises at least one of La, Ce, Pm, Sm, Gd, Tb, Tm, Lu, Sc, Y, Ag, Pt, Cu, and Ti;
wherein the molar ratio of the active component calculated by the metal element to the silicon-containing carrier calculated by Si is 0.01-0.5: 1.
according to the mesoporous catalyst provided by the invention, at least part of active components of the mesoporous catalyst are embedded into the framework of the silicon-containing carrier, so that the active sites of the active components are increased, and the methane oxidative coupling reaction is promoted.
In a second aspect of the present invention, there is provided a method for preparing a mesoporous catalyst, the method comprising:
(1) under an acidic condition, contacting a template agent, a silicon source and a first solvent, and then carrying out first drying to obtain a mesoporous material template;
(2) in the presence of a second solvent, mixing a precursor of an active component with the mesoporous material template, and then sequentially carrying out second drying and roasting to obtain a mesoporous catalyst;
wherein the metal element in the precursor of the active component is at least one of La, Ce, Pm, Sm, Gd, Tb, Tm, Lu, Sc, Y, Ag, Pt, Cu and Ti;
the molar ratio of the active component in terms of metal elements to the silicon-containing carrier in terms of Si in the obtained mesoporous catalyst is 0.01-0.5 by using the precursors of the active component and the silicon source: 1.
in a third aspect of the present invention, a mesoporous catalyst is provided, and the mesoporous catalyst is prepared by the above method.
In a fourth aspect of the present invention, there is provided a process for producing a hydrocarbon above carbon dioxide from methane, the process comprising: in the presence of oxygen, methane is contacted with the mesoporous catalyst to carry out catalytic reaction;
or preparing the mesoporous catalyst according to the method, and then contacting methane with the obtained mesoporous catalyst in the presence of oxygen to perform catalytic reaction.
According to the method for preparing the mesoporous catalyst, the mesoporous material template is prepared firstly, and then the precursor of the active component is mixed with the mesoporous material template in the presence of the second solvent to prepare the mesoporous catalyst, so that at least part of the active component is embedded into the framework of the silicon-containing carrier, and the active site of the active component is increased.
The method for preparing the carbon dioxide and the above hydrocarbons by the methane has the advantages that the methane is contacted with the mesoporous catalyst in the presence of oxygen to carry out catalytic reaction to prepare the carbon dioxide and the above hydrocarbons, the mesoporous catalyst can ensure that the reaction for preparing the carbon dioxide and the above hydrocarbons by the methane can be carried out at lower temperature (such as 450-520 ℃), the requirements on a reactor and operation conditions are reduced, and the method has higher methane conversion rate and higher selectivity of the hydrocarbons above carbon dioxide, and is more beneficial to industrial amplification production.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a mesoporous catalyst obtained in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a mesoporous catalyst, which comprises a silicon-containing carrier and an active component, wherein at least part of the active component is embedded into a framework of the silicon-containing carrier, and the active component comprises at least one of La, Ce, Pm, Sm, Gd, Tb, Tm, Lu, Sc, Y, Ag, Pt, Cu and Ti;
wherein the molar ratio of the active component calculated by the metal element to the silicon-containing carrier calculated by Si is 0.01-0.5: 1.
in some embodiments of the present invention, it is preferred that the molar ratio of the active component, calculated as the metal element, to the silicon-containing carrier, calculated as Si, is from 0.06 to 0.3: 1.
in some embodiments of the present invention, the specific surface area, pore volume and pore diameter of the mesoporous catalyst can be measured according to a nitrogen adsorption method, the specific surface area is calculated by using a BET method, and the pore volume is calculated by using a BJH model. The specific surface area of the mesoporous catalyst is preferably 400-600m2Per g, more preferably420-520m2(ii) in terms of/g. The pore volume of the mesoporous catalyst is preferably 0.8-1.2cm3In g, more preferably 1 to 1.09cm3(ii) in terms of/g. The average pore diameter of the mesoporous catalyst is preferably 2-5nm, and more preferably 2-3 nm.
In some embodiments of the invention, the active component is present in an oxidized form.
A second aspect of the present invention provides a method for preparing a mesoporous catalyst, the method comprising:
(1) under an acidic condition, contacting a template agent, a silicon source and a first solvent, and then carrying out first drying to obtain a mesoporous material template;
(2) in the presence of a second solvent, mixing a precursor of an active component with the mesoporous material template, and then sequentially carrying out second drying and roasting to obtain a mesoporous catalyst;
wherein the metal element in the precursor of the active component is at least one of La, Ce, Pm, Sm, Gd, Tb, Tm, Lu, Sc, Y, Ag, Pt, Cu and Ti;
the molar ratio of the active component in terms of metal elements to the silicon-containing carrier in terms of Si in the obtained mesoporous catalyst is 0.01-0.5 by using the precursors of the active component and the silicon source: 1.
in some embodiments of the present invention, preferably, the precursor of the active component and the silicon source are used in amounts such that the molar ratio of the active component calculated as the metal element to the silicon-containing carrier calculated as Si in the obtained mesoporous catalyst is 0.06-0.3: 1.
in some embodiments of the present invention, in the step (1), the long bond angle of the molecular sieve bond and the framework oxygen are regulated by using an acidic substance, and the pH value for controlling the acidic condition can be 2-5; the acidic substance is at least one of phosphoric acid, nitric acid, hydrochloric acid and acetic acid, and hydrochloric acid is preferred.
In some embodiments of the invention, the templating agent, which may be a nonionic surfactant, serves primarily as a structural template, structure directing, space filling, and framework charge balancing during the preparation process; preferably having the formula EOaPObEOaThe polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of (a); more preferably, wherein a has a value of 10 to 100, b has a value of 40 to 80; further preferred is EO20PO70EO20(ii) a Specifically, the source of the template agent is not limited in the present invention and may be obtained commercially (e.g., from Sigma-Aldrich under the trade name P123, formula EO)20PO70EO20) The compound can also be prepared by adopting a method in the prior art, and the details are not repeated here.
In some embodiments of the present invention, the kind of the silicon source is not particularly limited as long as the silicon element can be provided, and preferably, the silicon source may be sodium silicate and/or tetraethyl orthosilicate, and more preferably tetraethyl orthosilicate.
In some embodiments of the invention, the first solvent comprises water and an organic solvent (which may be an alcohol, in particular a saturated monohydric alcohol of C1-C6, preferably at least one selected from ethanol, propanol and butanol) in a weight ratio of 20-50: 1. the first solvent is preferably water and 1-butanol, more preferably deionized water and 1-butanol.
In some embodiments of the present invention, the templating agent, the silicon source, and the first solvent are used in amounts such that the molar ratio of the templating agent, the silicon source, and the first solvent is preferably 1: 50-500: 10050-: 50-200: 12000-14000.
In some embodiments of the invention, in step (1), the temperature of the contacting is preferably 80 to 120 ℃. The contact time is preferably 12 to 60 hours.
In some embodiments of the present invention, in step (1), there is no limitation on the conditions of the primary drying, and preferably, the temperature of the primary drying is preferably 80 to 120 ℃. The time of the first drying is preferably 12 to 30 hours.
In some embodiments of the invention, in step (1), the contacting is by: adding a silicon source into the template under the stirring condition (the stirring speed can be 200-800 r/min), wherein the adding speed of the silicon source can be 0.1-1g/min, preferably 0.1-0.5g/min based on 1g of the template, stirring for 12-36h, preferably 12-25h at 30-35 ℃ after the adding is finished, and then aging for 12-24h at the temperature of 80-120 ℃.
In some embodiments of the present invention, in step (1), the method further comprises washing the solid product after the first drying, and performing a third drying, wherein the temperature of the third drying is preferably 80-120 ℃, and the time of the third drying is preferably 12-18h, so as to obtain the mesoporous material template. The washing is carried out by adopting ethanol and/or hydrochloric acid for 3-5 times, and the mass concentration of the hydrochloric acid used in the washing is 5-10 wt%.
In the invention, the product (namely the mesoporous material template) obtained by drying in the step (1) is directly used for mixing and roasting with the active component precursor in the step (2), and the step of roasting is not included in the step (1).
In some embodiments of the present invention, in step (2), the second solvent may be water and/or ethanol. When the second solvent is water, the mixing is performed under alkaline conditions in order to control the morphology of the precipitated material. The pH value of the alkaline condition controlled by the alkaline substance is preferably 8 to 13, more preferably 10 to 13; the alkaline substance is at least one of sodium hydroxide, sodium bicarbonate and sodium carbonate, and is preferably sodium hydroxide. When the second solvent is ethanol, no special requirement is imposed on the pH value of the mixture, namely, no special control of the pH value is required.
In some embodiments of the present invention, in step (2), the mixing may be performed under stirring conditions (the stirring rate may be 200 revolutions per minute).
In some embodiments of the present invention, in the step (2), the mesoporous material template is preferably used in an amount of 30 to 200 parts by weight, more preferably 30 to 60 parts by weight, with respect to 100 parts by weight of the precursor of the active component.
In some embodiments of the present invention, in the step (2), the precursor of the active component preferably includes at least one of a La precursor, a Ce precursor, a Pm precursor, a Sm precursor, a Gd precursor, a Tb precursor, a Tm precursor, a Lu precursor, a Sc precursor, a Y precursor, an Ag precursor, a Pt precursor, a Cu precursor, and a Ti precursor.
In some embodiments of the present invention, in step (2), the precursor of the active component is preferably a water-soluble metal salt, more preferably a nitrate.
In some embodiments of the invention, in step (2), the temperature of the mixing is preferably 35 to 50 ℃. The mixing time is preferably 24-50 h.
In some embodiments of the present invention, in step (2), the temperature of the second drying is preferably 100-120 ℃, and the time of the second drying is preferably 2-3 h.
In the present invention, the solid-liquid separation step is generally included before the drying, and the solid phase obtained is subjected to subsequent drying, and the solid-liquid separation can be performed by a conventional manner (such as filtration), which is not described herein again.
In some embodiments of the present invention, in step (2), the temperature of the calcination is preferably 400-550 ℃, the calcination time is preferably 4-6h, and the temperature increase rate of the calcination is preferably 1-5 ℃/min, more preferably 1-2 ℃/min.
In the invention, in order to further improve the catalytic effect of the catalyst, the method can further comprise a step of washing the solid product after roasting is completed, preferably, the solid product obtained after roasting is washed three times by using 1-2mol/L sodium hydroxide solution, centrifuged to remove the supernatant, washed and precipitated to be neutral, and then subjected to fourth drying at 50-80 ℃ for 12-20 h.
In the present invention, the method may further include a step of shaping the resulting mesoporous catalyst. The forming method is not limited, and conventional extrusion forming can be adopted, and the obtained formed mesoporous catalyst can be cylindrical, honeycomb or sheet. Then crushing and screening the formed mesoporous catalyst, wherein the particle size of the obtained mesoporous catalyst is 40-60 meshes.
In a third aspect of the present invention, a mesoporous catalyst is provided, and the mesoporous catalyst is prepared by the above method.
In a fourth aspect of the present invention, there is provided a process for producing a hydrocarbon above carbon dioxide from methane, the process comprising: in the presence of oxygen, methane is contacted with the mesoporous catalyst to carry out catalytic reaction;
or preparing the mesoporous catalyst according to the method, and then contacting methane with the obtained mesoporous catalyst in the presence of oxygen to perform catalytic reaction.
In the present invention, the catalytic reaction may be performed in a continuous flow reactor, and the type of the continuous flow reactor is not limited in the present invention, and may be a fixed bed reactor, a stacked bed reactor, a fluidized bed reactor, a moving bed reactor, or a bubbling bed reactor. In particular, the mesoporous catalyst may be arranged in layers in a continuous flow reactor (e.g., a fixed bed) or mixed with a reactant stream (e.g., an ebullating bed).
In some embodiments of the present invention, in order to promote the catalytic reaction, increase the conversion of methane and increase the selectivity of hydrocarbons containing carbon and above, the molar ratio of the amounts of methane and oxygen is 1-10: 1, preferably 2 to 8: 1;
in some embodiments of the present invention, the conditions of the catalytic reaction are not particularly limited and may be selected conventionally in the art, and preferably, the reaction activation temperature of the catalytic reaction is 450-520 ℃; the time of the catalytic reaction is 1-10 h; the pressure of the catalytic reaction is 0.005-0.5MPa, and the space velocity of methane is 10000-100000 mL/(g.h), preferably 25000-80000 mL/(g.h).
In the present invention, the carbon and above hydrocarbons are selected from at least one of ethane, ethylene, propane and propylene.
In the present invention, the unit "mL/(g.h)" is the amount (mL) of the total gas of methane and oxygen used at a time of 1 hour, relative to 1g of the catalyst by mass.
In the present invention, the pressure means a gauge pressure.
The present invention will be described in detail below by way of examples.
In the examples and comparative examples, the reagents used were all commercially available analytical reagents. The drying box is produced by Shanghai-Hengchang scientific instruments Co., Ltd, and has the model of DHG-9030A. The muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100. Polyoxyethylene-polyoxyThe propylene-polyoxyethylene triblock copolymer is purchased from Sigma-Aldrich company under the trade name P123 and has the molecular formula of EO20PO70EO20And the molecular weight is 5800. Tetraethyl orthosilicate, analytically pure, purchased from Shanghai Allantin Biotechnology Ltd. The pH value during the experiment was measured using a Mettler pH meter S220.
Preparation example 1
Hydrochloric acid with the mass concentration of 37 wt% is added into a solution (the pH value is 3.8) consisting of 32g (0.006mol) of template agent P123 and 1300g of deionized water, stirring is carried out to completely dissolve the P123, 34g of 1-butanol is added into the solution, stirring is carried out for 2h at 35 ℃, 64.5g of tetraethyl orthosilicate is added into the solution at the rate of 0.1g/min, stirring is carried out for 24h at the temperature of 35 ℃, then the solution is heated to 100 ℃ and aged for 24 h. And filtering and separating a solid product while the solid product is hot, drying the solid product (the drying temperature is 100 ℃ and the drying time is 12 hours), washing the solid product for 3 times by using hydrochloric acid, wherein the mass concentration of the hydrochloric acid is 10 wt%, and drying the solid product in an oven (the temperature is 100 ℃ and the drying time is 18 hours) to obtain the mesoporous material template.
Example 1
Weighing 20g (0.046mol) of lanthanum nitrate hexahydrate, adding into 500g of absolute ethyl alcohol, and stirring until the lanthanum nitrate hexahydrate is completely dissolved; adding 10g of the mesoporous material template prepared in preparation example 1 into the uniformly mixed solution at 40 ℃, vigorously stirring (stirring speed is 500 rpm) for 24h, then putting the mixed solution into a water bath at 80 ℃ for 15h under the condition of stirring (stirring speed is 150 rpm), putting the solid product into an oven for drying (drying temperature is 110 ℃ and time is 2h), then putting the dried product into a muffle furnace, setting the temperature rise rate to be 1 ℃/min and the temperature to be 550 ℃, and roasting for 4h to obtain the mesoporous catalyst.
Example 2
Weighing 20g (0.046mol) of lanthanum nitrate hexahydrate, adding into 500g of absolute ethyl alcohol, and stirring until the lanthanum nitrate hexahydrate is completely dissolved; adding 40g of the mesoporous material template prepared in preparation example 1 into the uniformly mixed solution at 45 ℃, vigorously stirring (stirring speed is 600 revolutions per minute) for 24 hours, then carrying out water bath on the mixed solution at 85 ℃ for 12 hours under the condition of stirring (stirring speed is 200 revolutions per minute) to obtain a solid product, placing the solid product into an oven for drying (drying temperature is 110 ℃, time is 2 hours), then placing the solid product into a muffle furnace, setting the temperature rise rate to be 1 ℃/min and the temperature to be 550 ℃, and roasting for 4 hours to obtain the mesoporous catalyst.
Example 3
Weighing 20g (0.046mol) of lanthanum nitrate hexahydrate, adding into 500g of absolute ethyl alcohol, and stirring until the lanthanum nitrate hexahydrate is completely dissolved; adding 6g of the mesoporous material template prepared in preparation example 1 into the uniformly mixed solution at 35 ℃, vigorously stirring (stirring speed is 400 rpm) for 24 hours, then carrying out water bath on the mixed solution at 90 ℃ for 13 hours under the condition of stirring (stirring speed is 300 rpm) to obtain a solid product, placing the solid product into an oven for drying (drying temperature is 110 ℃, time is 2 hours), placing the solid product into a muffle furnace, setting the temperature rise rate to be 2 ℃/min and the temperature to be 550 ℃, and roasting for 4 hours to obtain the mesoporous catalyst.
Comparative example 1
A mesoporous catalyst was prepared according to the method of example 1, except that the mesoporous material template obtained in preparation example 1 was calcined in a muffle furnace at 550 ℃ for 6 hours to obtain a mesoporous material, and then the mesoporous material was used to replace the mesoporous material template in example 1 for the next experiment.
Comparative example 2
A mesoporous catalyst was prepared as in example 1, except that lanthanum nitrate hexahydrate was replaced with an equimolar amount of aluminum nitrate nonahydrate.
Comparative example 3
A mesoporous catalyst was prepared according to the method of example 1, except that lanthanum nitrate hexahydrate was used in an amount of 0.5 g.
Test example 1
0.1g of the mesoporous catalyst obtained in examples and comparative examples was charged in a fixed bed reactor and subjected to oxidative coupling with methane to produce carbon dioxide and the above hydrocarbons, the temperature of the site where the reaction material and the bed were in contact was monitored by thermal coupling and measured, the reaction products were detected at a series of temperatures of 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 502 ℃, 504 ℃, 506 ℃, 508 ℃, 510 ℃, 512 ℃, 514 ℃, 516 ℃, 518 ℃, 520 ℃, 522 ℃, 524 ℃, 526 ℃, 528 ℃, 530 ℃, 535 ℃, 540 ℃, 545 ℃ and 550 ℃, and the reaction activation temperature of the catalytic reaction (i.e., the temperature of the catalyst bed at which the reaction product was detected by gas chromatography to have the formation of any of the above-mentioned hydrocarbons) was measured as shown in Table 1, the contact pressure was 0.01MPa, and the methane: the molar ratio of oxygen is 2: 1, the contact time is 4h, the space velocity of methane is 30000 mL/(g.h), and the reaction product is collected after the reaction.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A. Wherein, hydrocarbons such as methane, ethane, ethylene, propane, propylene and the like are detected by an alumina column FID detector, methane, carbon monoxide, carbon dioxide and oxygen are detected by a carbon molecular sieve column TCD detector, and the calculation is carried out by a carbon balance method.
The methane conversion and the like are calculated as follows:
methane conversion ═ amount of methane consumed by the reaction/initial amount of methane × 100%
Ethylene selectivity is the amount of methane consumed by ethylene produced/total consumption of methane × 100%
Ethane selectivity is the amount of methane consumed by ethane produced/total consumption of methane × 100%
Propane selectivity is the amount of methane consumed by the propane formed/total consumption of methane x 100%
Propylene selectivity is the amount of methane consumed by propylene produced/total consumption of methane × 100%
Selective yield of hydrocarbons over carbon two ═ ethane selectivity + ethylene selectivity + propylene selectivity + propane selectivity
The results obtained are shown in table 1.
Test example 2
Nitrogen desorption experiments of mesoporous catalyst samples obtained in examples and comparative examples were performed on a fully automatic physical chemical adsorption analyzer model ASAP2020M + C manufactured by Micromeritics, usa. The samples were degassed at 350 ℃ for 4 hours under vacuum prior to assay. The specific surface area of the sample was calculated by the BET method, and the pore volume and the average pore diameter were calculated by the BJH model, and the results are shown in table 1.
Test example 3
Elemental analysis methods of mesoporous catalysts in examples and comparative examples contents were measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES) having an instrument model of fisher iCAP 6500 analyzer, and the test results are shown in table 1.
Test example 4
The mesoporous catalyst sample obtained in the embodiment is subjected to nuclear magnetic resonance testing, and a testing instrument is an AVANCE 400MHz III digital nuclear magnetic resonance spectrometer of Bruker company; a5 mm sample tube was used for the test, the resonance frequency was 79.495MHz, the MAS revolution number was 8kHz, and the chemical shift reference was tetramethylsilane. The test results show that the peak positions of the nuclear magnetic resonance spectrograms of the mesoporous catalysts obtained in examples 1-3 are shifted relative to pure KIT-6 and appear at the-101 ppm position, the main peak position of the pure KIT-6 molecular sieve is shown at the-99 ppm position, and the change of the chemical shift indicates that the metal element lanthanum is doped into the framework of the KIT-6 molecular sieve. The NMR spectrum obtained in example 1 is shown in FIG. 1.
TABLE 1
As can be seen from Table 1, when the mesoporous catalysts obtained in examples 1-3 and comparative examples 1-3 are used in the oxidative coupling reaction of methane, the methane conversion rate and the selectivity of hydrocarbon over carbon can be maintained at a high level after 4 hours of reaction in examples 1-3, and the catalytic reaction activation temperatures in examples 1-3 are 500 ℃, 510 ℃ and 506 ℃ respectively; after the reaction time of comparative examples 1 to 3 is 4 hours, the methane conversion rate and the selectivity of hydrocarbon above carbon dioxide are reduced compared with those of examples 1 to 3, and the catalytic reaction activation temperatures of comparative examples 1 to 3 are respectively 520 ℃, 750 ℃ and 660 ℃ which are higher than those of examples 1 to 3, which shows that the mesoporous catalyst of the invention has lower catalytic reaction activation temperature and excellent stability, and is beneficial to industrial scale-up production.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A mesoporous catalyst is characterized by comprising a silicon-containing carrier and an active component, wherein at least part of the active component is embedded into the framework of the silicon-containing carrier, and the active component comprises at least one of La, Ce, Pm, Sm, Gd, Tb, Tm, Lu, Sc, Y, Ag, Pt, Cu and Ti;
wherein the molar ratio of the active component calculated by the metal element to the silicon-containing carrier calculated by Si is 0.01-0.5: 1.
2. the mesoporous catalyst according to claim 1, wherein the mesoporous catalyst has a specific surface area of 400-600m2G, preferably 420-520m2/g；
And/or the pore volume of the mesoporous catalyst is 0.8-1.2cm3In g, preferably 1 to 1.09cm3/g；
And/or the average pore diameter of the mesoporous catalyst is 2-5nm, preferably 2-3 nm;
and/or, the active component is present in the form of an oxidation state;
and/or the molar ratio of the active component calculated by the metal element to the silicon-containing carrier calculated by Si is 0.06-0.3: 1.
3. a method of preparing a mesoporous catalyst, the method comprising:
(1) under an acidic condition, contacting a template agent, a silicon source and a first solvent, and then carrying out first drying to obtain a mesoporous material template;
(2) in the presence of a second solvent, mixing a precursor of an active component with the mesoporous material template, and then sequentially carrying out second drying and roasting to obtain a mesoporous catalyst;
wherein the metal element in the precursor of the active component is at least one of La, Ce, Pm, Sm, Gd, Tb, Tm, Lu, Sc, Y, Ag, Pt, Cu and Ti;
the molar ratio of the active component in terms of metal elements to the silicon-containing carrier in terms of Si in the obtained mesoporous catalyst is 0.01-0.5 by using the precursors of the active component and the silicon source: 1.
4. the method according to claim 3, wherein, in the step (1), the acidic condition is controlled to have a pH value of 2 to 5 using an acidic substance; the acidic substance is at least one of phosphoric acid, nitric acid, hydrochloric acid and acetic acid, and is preferably hydrochloric acid;
and/or, the template agent is a nonionic surfactant; preferably having the formula EOaPObEOaThe polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of (a); more preferably, wherein a is 10-100, b is 40-80; EO is particularly preferred20PO70EO20；
And/or the silicon source is sodium silicate and/or tetraethyl orthosilicate, preferably tetraethyl orthosilicate;
and/or, the first solvent comprises water and an organic solvent; preferably water and 1-butanol, more preferably deionized water and 1-butanol;
and/or the template agent, the silicon source and the first solvent are used in such amounts that the molar ratio of the template agent, the silicon source and the first solvent is 1: 50-500: 10050-: 50-200: 12000-14000.
5. The process according to claim 3, wherein in step (1), the contacting is carried out at a temperature of 80-120 ℃ for a time of 12-60 h;
and/or the temperature of the first drying is 80-120 ℃, and the time is 12-30 h;
and/or, the contact mode is as follows: adding a silicon source into a template agent under the stirring condition, wherein the adding rate of the silicon source is 0.1-1g/min, preferably 0.1-0.5g/min based on 1g of the template agent, stirring for 12-36h, preferably 12-25h at 30-35 ℃ after the adding is finished, and then aging for 12-24h at 80-120 ℃;
and/or, the method also comprises the steps of washing the first dried solid product, and then carrying out third drying, so as to obtain the mesoporous material template, wherein the temperature of the third drying is 80-120 ℃, and the time is 12-18 h.
6. The method according to claim 3, wherein, in step (2), the second solvent is water and/or ethanol; when the second solvent is water, the mixing is carried out under alkaline conditions, and the pH value of the alkaline conditions is controlled to be 8-13, preferably 10-13 by using alkaline substances; the alkaline substance is at least one of sodium hydroxide, sodium bicarbonate and sodium carbonate, and is preferably sodium hydroxide;
and/or, the mesoporous material template is used in an amount of 30-200 parts by weight, preferably 30-60 parts by weight, relative to 100 parts by weight of the precursor of the active component;
and/or the precursor of the active component comprises at least one of a La precursor, a Ce precursor, a Pm precursor, a Sm precursor, a Gd precursor, a Tb precursor, a Tm precursor, a Lu precursor, a Sc precursor, a Y precursor, an Ag precursor, a Pt precursor, a Cu precursor and a Ti precursor;
and/or the precursor of the active component is water-soluble metal salt, more preferably nitrate;
and/or the precursor of the active component and the silicon source are used in such an amount that the molar ratio of the active component calculated by the metal element to the silicon-containing carrier calculated by Si in the obtained mesoporous catalyst is 0.06-0.3: 1.
7. the method according to claim 3 or 6, wherein, in step (2), the temperature of the mixing is 35-50 ℃; the mixing time is 24-50 h;
and/or the temperature of the second drying is 100-120 ℃, and the time is 2-3 h;
and/or the roasting temperature is 400-550 ℃, the time is 4-6h, and the roasting temperature rise rate is 1-5 ℃/min, preferably 1-2 ℃/min.
8. A mesoporous catalyst, characterized in that it is prepared by the method of any one of claims 3-7.
9. A method for producing a hydrocarbon containing more than two carbon atoms from methane, the method comprising: contacting methane with the mesoporous catalyst of any one of claims 1, 2 and 8 in the presence of oxygen to perform a catalytic reaction;
or preparing a mesoporous catalyst according to the method of any one of claims 3 to 7, and then contacting methane with the obtained mesoporous catalyst in the presence of oxygen to perform catalytic reaction.
10. The process according to claim 9, characterized in that the molar ratio between the quantities of methane and oxygen is between 1 and 10: 1, preferably 2 to 8: 1;
and/or the reaction activation temperature of the catalytic reaction is 450-520 ℃; the time of the catalytic reaction is 1-10 h; the pressure of the catalytic reaction is 0.005-0.5MPa, and the space velocity of methane is 10000-100000 mL/(g.h), preferably 25000-80000 mL/(g.h).
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