CN115487853B - Mixed catalyst containing lanthanum oxide carbonate and silver loaded molecular sieve, and preparation method and application thereof - Google Patents
Mixed catalyst containing lanthanum oxide carbonate and silver loaded molecular sieve, and preparation method and application thereof Download PDFInfo
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- CN115487853B CN115487853B CN202110678755.7A CN202110678755A CN115487853B CN 115487853 B CN115487853 B CN 115487853B CN 202110678755 A CN202110678755 A CN 202110678755A CN 115487853 B CN115487853 B CN 115487853B
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- molecular sieve
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- lanthanum
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- lanthanum oxide
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 88
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 70
- 239000004332 silver Substances 0.000 title claims abstract description 70
- KGDJAQAMSDMZCD-UHFFFAOYSA-M hydrogen carbonate lanthanum(3+) oxygen(2-) Chemical compound C([O-])(O)=O.[O-2].[La+3] KGDJAQAMSDMZCD-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 40
- 229910052746 lanthanum Inorganic materials 0.000 claims description 32
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229940100890 silver compound Drugs 0.000 claims description 7
- 150000003379 silver compounds Chemical class 0.000 claims description 7
- 150000002603 lanthanum Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 11
- 229910001961 silver nitrate Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- 239000011343 solid material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 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 3
- 241000252206 Cypriniformes Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ARJFOGOIGWNNPB-UHFFFAOYSA-N [C].O1CCOCC1 Chemical compound [C].O1CCOCC1 ARJFOGOIGWNNPB-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MCYSFVUDODFQPV-UHFFFAOYSA-K lanthanum(3+) trichlorate Chemical compound [La+3].[O-][Cl](=O)=O.[O-][Cl](=O)=O.[O-][Cl](=O)=O MCYSFVUDODFQPV-UHFFFAOYSA-K 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, in particular to a mixed catalyst containing lanthanum oxide carbonate and silver loaded molecular sieve, and a preparation method and application thereof. The mixed catalyst comprises lanthanum oxide carbonate and a silver-loaded molecular sieve; wherein the molecular sieve is selected from one or more of TS-1, SBA-15, KIT-6, silicalite-1 and Silicalite-2. According to the technical scheme, lanthanum oxide carbonate is adopted as the first active component, silver is uniformly loaded on the molecular sieve, and then the molecular sieve loaded with silver is uniformly mixed with lanthanum oxide carbonate, so that the lanthanum oxide carbonate mixed methane oxidative coupling reaction catalyst capable of effectively reducing temperature rise caused by bed heat release is prepared.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a mixed catalyst containing lanthanum oxide carbonate and silver loaded molecular sieve, and a preparation method and application thereof.
Background
In recent years, natural gas resources are found and mined on a large scale, and the production of ethylene and downstream products thereof as raw materials is becoming more and more important in the industry due to the low price and relatively abundant reserves.
In terms of technical principle, the direct conversion of methane to ethylene is mainly divided into two technical routes:
(1) Methane oxidative coupling to ethylene (OCM): methane first forms methyl radicals under catalysis, and then under aerobic conditions, the methyl radicals are coupled to produce ethylene and water. The technology developed by Shanxi coal institute of Chinese sciences, zhuang Xinmo Feng and Luan An co-operation belongs to the route.
(2) Preparing ethylene by methane anaerobic coupling: methane first forms methyl radicals under catalysis, and then under anaerobic conditions, the methyl radicals are coupled to produce ethylene and hydrogen. Bao Xin and the technology studied by the institutes belong to the technical route. The anaerobic conversion of methane can be realized only at the temperature of more than 1000 ℃, and the product is mainly aromatic hydrocarbon, but carbon is easy to be deposited in the process, and the industrial realization is difficult due to the too high temperature.
The reaction temperature of the ethylene prepared by the oxidative coupling of methane is relatively low, along with the continuous progress of the material preparation level and means, the reaction starting temperature can be reduced to 600 ℃ or below, a path is further opened for industrial application, the oxidative coupling of methane is a strong exothermic reaction, the heat release at the position of a catalyst bed layer is particularly obvious, the local temperature of a reactor is easy to rise, the difficulty is brought to the control of a reaction process, and the industrial application difficulty of the technology can be reduced if the local heat release of the catalyst bed layer can be effectively reduced.
Disclosure of Invention
The invention aims to solve the problem of partial heat release of a catalyst bed in the prior art and provides a mixed catalyst containing lanthanum oxide carbonate and a silver-loaded molecular sieve, and a preparation method and application thereof. The catalyst provided by the invention can effectively reduce the local heat release of the catalyst bed.
In order to achieve the above object, in a first aspect, the present invention provides a mixed catalyst comprising lanthanum oxycarbonate and a silver-supported molecular sieve;
wherein the molecular sieve is selected from one or more of TS-1, SBA-15, KIT-6, silicalite-1 and Silicalite-2.
In a second aspect, the present invention provides a method of preparing a hybrid catalyst, the method comprising: mixing lanthanum oxide carbonate and a silver-loaded molecular sieve to obtain the mixed catalyst;
wherein the molecular sieve is selected from one or more of TS-1, SBA-15, KIT-6, silicalite-1 and Silicalite-2.
In a third aspect, the present invention provides a hybrid catalyst prepared by the method described above.
In a fourth aspect, the present invention provides the use of a hybrid catalyst as described above in the oxidative coupling of methane.
In a fifth aspect, the present invention provides a process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with a mixed catalyst as described above in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, a mixed catalyst is prepared as described above, and then methane is contacted with the resulting mixed catalyst in the presence of oxygen and under conditions of oxidative coupling of methane.
According to the technical scheme, lanthanum oxide carbonate is adopted as the first active component, silver is uniformly loaded on the molecular sieve, and then the molecular sieve loaded with silver is uniformly mixed with lanthanum oxide carbonate, so that the lanthanum oxide carbonate mixed methane oxidative coupling reaction catalyst capable of effectively reducing the temperature rise caused by bed heat release is prepared, and the temperature rise of the reaction bed is changed along with the change of reaction conditions.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a hybrid catalyst comprising lanthanum oxycarbonate and a silver-loaded molecular sieve;
wherein the molecular sieve is selected from one or more of TS-1, SBA-15, KIT-6, silicalite-1 and Silicalite-2.
In the invention, TS-1 is a titanium-silicon molecular sieve, belongs to Pentasil heteroatom molecular sieve, is in an orthorhombic system, has a three-dimensional pore structure represented by ZSM-5, consists of Z-shaped channels and elliptic straight channels intersected with the Z-shaped channels, and four coordinated Ti in a frame is an active center for selective oxidation reaction, and besides the topological structure of the original MFI molecular sieve is maintained, TS-1 forms skeleton Si-O-Ti bonds with special properties due to uniform distribution of titanium atoms in the skeleton. It is commercially available or can be prepared by itself according to a known method, and the present invention is not particularly limited thereto.
In the invention, SBA-15 belongs to one of mesoporous molecular sieves, has a two-dimensional hexagonal through hole structure and has a P6mm space group. In the XRD diffraction pattern, the main peak is around 1 DEG, and is a (10) crystal plane peak. The next highest peak is in turn the peak (11) and the peak (20). Other peaks are weaker and less visible. In addition, the silica on the SBA-15 framework is generally amorphous and no significant diffraction peaks are observed in wide angle XRD diffraction. It is commercially available or can be prepared by itself according to a known method, and the present invention is not particularly limited thereto.
In the invention, KIT-6 belongs to one of mesoporous molecular sieves, has a three-dimensional cubic ordered structure, has an adjustable aperture of 4-12nm, can be obtained commercially, can be prepared by a known method, and is not particularly limited.
In the present invention, silicalite-1 and Silicalite-2 are pure silicon molecular sieves composed of only silicon and oxygen, have a very stable structure, have small ionic activity, are commercially available, and can be prepared by themselves according to a well-known method, and the present invention is not particularly limited thereto. Silicalite-1 is used herein in the literature Laprune, D.; tuel, A.; fargusseng, d.; meunier, F.C., selective removal of external Ni nanoparticles onNi@Silicalite-1single crystal nanoboxes:Application to size-selective electrode hydrogenation, applied Catalysis A: general 2017,535,69-76. Report methods. Silicalite-2 was used in literature Dong, J.; zou, j.; long, Y., synthesis and characterization of colloidal TBA-Silicalite-2.Microporous Mesoporous Mater.2003,57 (1), 9-19.
Preferably, in the silver-loaded molecular sieve, the weight ratio of the silver element loading to the molecular sieve is 0.01-0.5:1, more preferably 0.025-0.25:1.
Wherein the silver-loaded molecular sieve may be prepared according to methods known in the art, preferably according to methods described in detail in the second aspect below.
Preferably, in the mixed catalyst, the weight ratio of lanthanum oxycarbonate to silver-loaded molecular sieve is 1:0.01-100, more preferably 1:0.1-10, and even more preferably 1:0.2-8.
In the present invention, the morphology of lanthanum oxycarbonate is not particularly limited, and for example, lanthanum oxycarbonate having different morphologies may be prepared according to a method well known in the art, and may be selected from at least one of a block, a sheet, a flower, a rod, and a needle.
Preferably, the lanthanum oxycarbonate is nanoscale in at least one dimension.
In the present invention, the shape of the mixed catalyst is not particularly limited, and for example, the mixed catalyst is in the form of powder or has at least one of a granular shape, a hexagonal shape, a hollow shape and a plate shape.
In a second aspect, the present invention provides a method of preparing a hybrid catalyst, the method comprising: mixing lanthanum oxide carbonate and a silver-loaded molecular sieve to obtain the mixed catalyst;
wherein the molecular sieve is selected from one or more of TS-1, SBA-15, KIT-6, silicalite-1 and Silicalite-2.
Wherein the molecular sieve; in the silver-loaded molecular sieve, the weight ratio of the load of silver element to the molecular sieve; in the mixed catalyst, the weight ratio of lanthanum oxide carbonate to silver loaded molecular sieve; the morphology of lanthanum oxycarbonate has been described in detail in the first aspect above, and will not be repeated here.
According to a preferred embodiment of the present invention, the method for preparing a silver-loaded molecular sieve comprises: and dissolving a silver compound precursor, loading the silver compound precursor on a molecular sieve by an impregnation method, and sequentially carrying out first drying and first roasting on the obtained material after loading to obtain the silver loaded molecular sieve.
Wherein the silver compound precursor may be any soluble salt that provides elemental silver, preferably selected from the group consisting of silver nitrate, silver chloride and silver acetate.
Preferably, the concentration of the silver element in the solution after the dissolution of the silver compound precursor is 0.01 to 20 wt%, more preferably 0.1 to 15 wt%, still more preferably 0.5 to 6.5 wt%.
In the present invention, in order to promote dissolution of the compound precursor of silver, the dissolution may be performed under heating, and the heating temperature may be 40 to 80 ℃.
In the present invention, in order to promote dissolution of the silver compound precursor, the dissolution may be performed under stirring.
Preferably, the impregnation is an isovolumetric impregnation. According to a preferred embodiment of the invention, the method of impregnation comprises: the solution of the silver-containing compound precursor is added dropwise to the sieve support for equal volume impregnation.
Wherein the dropping speed may be 10 to 50 drops/min with respect to 5g of the molecular sieve. It will be appreciated that the volume of 1 drop is typically about 0.05ml.
In the invention, the temperature of the first drying can be 60-120 ℃ and the time can be 12-30h.
According to a more preferred embodiment of the present invention, the first drying comprises stirring at 70-90 ℃ until the solvent volatilizes, and then drying at 100-120 ℃ for 10-15 hours.
Wherein the first drying may be performed in an oven.
In the present invention, the first firing temperature is 440 to 600 ℃, preferably 440 to 500 ℃, for 1 to 6 hours, preferably 1 to 4 hours.
Wherein the first calcination may be performed in a muffle furnace.
In the present invention, the lanthanum oxycarbonate is obtained by subjecting lanthanum hydroxide to the second calcination, and therefore, the morphology of the obtained lanthanum oxycarbonate depends on the morphology of lanthanum hydroxide as a raw material.
In the invention, the lanthanum oxide carbonate can also be prepared by taking water-soluble lanthanum salt as a starting material through a hydrothermal method.
According to a specific embodiment of the invention, the preparation method comprises the following steps:
dissolving water-soluble lanthanum salt in water, adding alkali liquor, continuously stirring for 3-10h (preferably 6-8 h) after the mixed liquor is changed into milky gel, and carrying out hydrothermal reaction on the obtained material;
and (3) sequentially centrifuging, washing, drying for the second time and roasting for the material subjected to the hydrothermal reaction to obtain nano lanthanum oxide carbonate.
In the present invention, the water-soluble lanthanum salt may be various conventionally used water-soluble lanthanum salts, and for example, may include, but is not limited to, lanthanum chloride, lanthanum chlorate and lanthanum nitrate.
Wherein the concentration of lanthanum element in the solution can be selected within a wide range, preferably, in order to obtain a catalyst with better performance, the concentration of lanthanum element in the solution is 0.05-10 wt%, preferably 0.1-5 wt%, more preferably 0.4-1 wt%.
In the present invention, the alkali solution may be a solution formed by conventional various alkali, and the alkali may be sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, etc.
Preferably, the concentration of the lye is 1-30% by weight, and the lye is added in an amount of 2-30ml, more preferably 4-23ml, relative to 100-350ml of the system.
According to a specific embodiment of the invention, the lye is a 20-30 wt.% ammonium hydroxide solution added in an amount of 2-6ml relative to 100-150ml of the system.
According to a specific embodiment of the invention, the lye is a 10-15 wt.% ammonium hydroxide solution and the sodium hydroxide solution is added in an amount of 8-23ml relative to 250-350ml of the system.
It can be appreciated that the addition of the lye is based on the conversion of the mixed system into a milky white gel.
In the present invention, the hydrothermal reaction conditions may be conventional hydrothermal reaction conditions, but preferably, the hydrothermal reaction conditions include: the temperature is 80-180deg.C, preferably 160-180deg.C, and the time is 12-120 hr, preferably 80-100 hr.
According to the invention, the separation method may be filtration, centrifugation, or the like. According to a preferred embodiment of the invention, the solid material is obtained by means of centrifugation. The centrifugation conditions preferably include: the rotation speed is 3000-10000rpm, preferably 5000-8500rpm; the time is 10-60min, preferably 15-20min.
According to the invention, the solid material is preferably, before it is dried, further washed, possibly with water and/or ethanol. According to a preferred embodiment of the invention, the washing is carried out with water (distilled water) 2-5 times and then with ethanol 1-2 times.
In the present invention, the temperature of the second drying may be changed within a wide range, and preferably, the temperature of the second drying is 60 to 180 ℃. Preferably 70-90 ℃.
In the present invention, the time of the second drying may vary within a wide range, and preferably, the time of the second drying is 10 to 50 hours, preferably 12 to 48 hours.
Wherein the second drying may be performed in an oven.
In the present invention, the temperature of the second firing may be varied within a wide range, and preferably, the temperature of the firing is 450 to 650 ℃, preferably 550 to 600 ℃.
In the present invention, the time of the second firing may be varied within a wide range, and preferably, the time of the firing is 2 to 8 hours, preferably 3 to 4 hours.
Wherein the second calcination may be performed in a muffle furnace.
In the present invention, the atmosphere of the second firing is not particularly limited, and may be an air atmosphere or a carbon dioxide atmosphere, or may be a nitrogen atmosphere, and preferably an air atmosphere or a carbon dioxide atmosphere.
In the invention, the method further comprises the following steps: the lanthanum oxide and silver-loaded molecular sieve are mixed in a powdery form, or are mixed in a form of at least one of a granular form, a hexagonal form, a hollow form and a sheet form, or are mixed in a powdery form and are formed into at least one of a granular form, a hexagonal form, a hollow form and a sheet form.
According to a preferred embodiment of the present invention, the preparation method of the mixed catalyst comprises:
(1) Preparation of lanthanum oxycarbonate
Accurately weighing lanthanum nitrate hexahydrate, dissolving in deionized water (lanthanum element concentration is 0.45-0.55 wt%), stirring until the solution is clear, adding 20-30 wt% ammonium hydroxide solution, changing the mixed solution into milky gel, continuously stirring at room temperature for 6-7h, finally transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining, statically aging at 170-180 ℃ for 80-85h, cooling the hydrothermal kettle to room temperature, centrifuging at 5000-5500rpm for 15-20min by a centrifuge, separating solid materials, washing with deionized water for 2-5 times, washing with ethanol for 1-3 times, drying the obtained solid at 85-90 ℃ for 12-15h, and roasting in air at 550-600 ℃ for 2-4h.
(2) Preparation of silver-loaded molecular sieves
Weighing 4-6g of SBA-15 molecular sieve, accurately weighing silver nitrate, dissolving in deionized water (the concentration of silver element is 1.5-2.5 wt%, and the mass ratio of silver element to molecular sieve is 0.05-0.07:1), stirring uniformly, then dripping silver nitrate solution onto SBA-15 molecular sieve (15-25 drops/min), adopting isovolumetric dipping, stirring uniformly, stirring in a 75-85 ℃ oven until the solvent volatilizes, then heating to 110-120 ℃ for 10-12h, transferring to a muffle furnace for 450-550 ℃ and keeping for 3-5h.
(3) Preparation of mixed catalysts
And uniformly mixing the prepared lanthanum oxide carbonate and the SBA-15 molecular sieve loaded with silver according to a ratio of 1:0.8-1.2 to prepare the catalyst.
In a third aspect, the present invention provides a hybrid catalyst prepared by the method described above.
In a fourth aspect, the present invention provides the use of a hybrid catalyst as described above in the oxidative coupling of methane.
In a fifth aspect, the present invention provides a process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with a mixed catalyst as described above in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, a mixed catalyst is prepared as described above, and then methane is contacted with the resulting mixed catalyst in the presence of oxygen and under conditions of oxidative coupling of methane.
In the present invention, the conditions for the oxidative coupling reaction of methane are not particularly limited and may be selected conventionally in the art, and the conditions for the oxidative coupling reaction of methane may include a reaction temperature of 400 to 800℃and a space velocity of methane of 5000 mL/(g.h) to 150000 mL/(g.h). Preferably, the molar ratio of methane to oxygen is 2-10:1.
the present invention will be described in detail by examples.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under the model number 7890A.
The methane conversion was calculated as follows:
methane conversion = amount of methane consumed by the reaction/initial amount of methane x 100%.
The ethylene selectivity was calculated as follows:
ethylene selectivity = amount of methane consumed by ethylene produced/total amount of methane consumed x 100%.
The ethane selectivity was calculated as follows:
ethane selectivity = amount of methane consumed by ethane produced/total consumption of methane x 100%.
The method for calculating the yield of the carbon dioxide is as follows:
carbon dioxane yield = methane conversion x (ethane selectivity + ethylene selectivity).
SBA-15 molecular sieves were purchased from Alatine, gauge: specific surface area (m 2/g): 433.8 pore size (nm): 4.2.
TS-1 molecular sieves were purchased from Jiu Ding Chemicals, cat# L-ML696.
KIT-6 molecular sieves were purchased from Jiu Ding Chemicals, cat No. L-LQ579.
Silicalite-1 was described in literature Laprune, D.; tuel, A.; fargusseng, d.; meunier, F.C., selective removal of external Ni nanoparticles on Ni@Silicalite-1single crystal nanoboxes:Application to size-selective electrode hydrogenation, applied Catalysis A: general 2017,535,69-76. Report methods.
Silicalite-2 was used in literature Dong, J.; zou, j.; long, Y., synthesis and characterization of colloidal TBA-Silicalite-2.Microporous Mesoporous Mater.2003,57 (1), 9-19.
Example 1
(1) Preparation of lanthanum oxycarbonate
Accurately weighing lanthanum nitrate hexahydrate, dissolving in 136g of deionized water (lanthanum element concentration is 0.50 wt%), stirring until the solution is clear, adding 4.7ml of 25 wt% ammonium hydroxide solution, changing the mixed solution into milky gel, continuously stirring at room temperature for 6h, finally transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining, statically aging at 180 ℃ for 80h, centrifuging at 5000rpm by a centrifuge after the hydrothermal kettle is cooled to room temperature, separating solid materials by centrifugation at 15min, washing three times by deionized water, washing twice by ethanol, drying the obtained solid at 90 ℃ for 12h, roasting in air at 600 ℃ for 3h, and preparing the nano lanthanum oxide carbonate, wherein the catalyst has a characteristic peak of lanthanum oxide carbonate by XRD characterization.
(2) Preparation of silver-loaded molecular sieves
Weighing 5g of SBA-15 molecular sieve, accurately weighing silver nitrate, dissolving in 15ml of deionized water (the concentration of silver element is 2.1 wt%, and the mass ratio of silver element to molecular sieve is 0.06:1), stirring uniformly, then dripping silver nitrate solution onto the SBA-15 molecular sieve (20 drops/min), adopting equal volume impregnation, stirring uniformly, stirring in an oven at 80 ℃ until the solvent volatilizes, heating to 120 ℃,10h, transferring to a muffle furnace, and maintaining at 500 ℃ for 4h.
(3) Preparation of mixed catalysts
And uniformly mixing 0.4g of prepared lanthanum oxide carbonate and 0.4g of silver-loaded SBA-15 molecular sieve to prepare the catalyst LAG-cat-1.
Example 2
(1) Preparation of lanthanum oxycarbonate
Accurately weighing lanthanum acetate, dissolving in 250g of deionized water (lanthanum element concentration is 0.55 wt%) and stirring until the solution is clear, adding 8ml of 15 wt% sodium hydroxide solution, changing the mixed solution into milky gel, continuously stirring at room temperature for 7h, finally transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining, statically aging at 160 ℃ for 100h, centrifuging at 8500rpm for 20min after the hydrothermal kettle is cooled to room temperature, separating solid materials by a centrifugal separator, washing with deionized water for three times, washing with ethanol for two times, drying the obtained solid at 80 ℃ for 24h, roasting at 600 ℃ for 4h in air, and obtaining nano lanthanum oxide carbonate, wherein the catalyst has characteristic peaks of lanthanum oxide carbonate by XRD characterization.
(2) Preparation of silver-loaded molecular sieves
5g of TS-1 molecular sieve is weighed, silver nitrate is accurately weighed and dissolved in 30ml of deionized water (the concentration of silver element is 0.64 wt%, the mass ratio of silver element to molecular sieve is 0.04:1), the mixture is stirred uniformly, then silver nitrate solution is dripped onto the TS-1 molecular sieve (30 drops/min), equal volume impregnation is adopted, the mixture is stirred uniformly, the mixture is stirred in a 75 ℃ oven until the solvent volatilizes, then the temperature is raised to 115 ℃ for 12 hours, and the mixture is transferred to a muffle furnace for 1 hour at 450 ℃.
(3) Preparation of mixed catalysts
And uniformly mixing 1g of prepared lanthanum oxide carbonate and 0.5g of TS-1 molecular sieve loaded with silver to prepare the catalyst LAG-cat-2.
Example 3
(1) Preparation of lanthanum oxycarbonate
Accurately weighing lanthanum chloride, dissolving in 300g of deionized water (lanthanum element concentration is 0.95 wt%) and stirring until the solution is clear, adding 15ml of 10 wt% ammonium hydroxide solution, changing the mixed solution into milky gel, continuously stirring at room temperature for 8h, finally transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining, statically aging at 170 ℃ for 90h, centrifuging to separate solid materials by a centrifugal separator at 7800rpm for 20min after the hydrothermal kettle is cooled to room temperature, washing with deionized water for three times, washing with ethanol for two times, drying the obtained solid at 70 ℃ for 12h, roasting at 550 ℃ for 4h in air, and obtaining nano lanthanum oxide carbonate, wherein the catalyst has characteristic peaks of lanthanum oxide carbonate by XRD characterization.
(2) Preparation of silver-loaded molecular sieves
Weighing 5g of KIT-6 molecular sieve, accurately weighing silver nitrate, dissolving in 15ml of deionized water (the concentration of silver element is 0.85 wt%, and the mass ratio of silver element to molecular sieve is 0.025:1), stirring uniformly, then dripping silver nitrate solution onto KIT-6 molecular sieve (50 drops/min), adopting equal volume dipping, stirring uniformly, stirring in a 70 ℃ oven until solvent volatilizes, heating to 100 ℃,15h, transferring to a muffle furnace, and maintaining at 440 ℃ for 2h.
(3) Preparation of mixed catalysts
And uniformly mixing 1g of prepared lanthanum oxide carbonate and 2g of silver-loaded KIT-6 molecular sieve to prepare the catalyst LAG-cat-3.
Example 4
(1) Preparation of lanthanum oxycarbonate
Accurately weighing lanthanum nitrate hexahydrate, dissolving in 350g of deionized water (the concentration of lanthanum element is 0.46 wt%) and stirring until the solution is clear, adding 23ml of 10 wt% ammonium hydroxide solution, changing the mixed solution into milky gel, continuously stirring at room temperature for 8h, finally transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining, statically aging at 160 ℃ for 80h, after the hydrothermal kettle is cooled to room temperature, centrifuging at 8500rpm for 15min to separate solid materials by a centrifugal separator, washing with deionized water for three times, washing with ethanol for two times, drying the obtained solid at 80 ℃ for 48h, roasting at 600 ℃ for 4h in air, and preparing the nano lanthanum oxide carbonate, wherein the catalyst has a characteristic peak of lanthanum oxide carbonate by XRD characterization.
(2) Preparation of silver-loaded molecular sieves
5g of Silicalite-1 molecular sieve is weighed, silver nitrate is accurately weighed and dissolved in 20ml of deionized water (the concentration of silver element is 6.35 wt%, the mass ratio of silver element to molecular sieve is 0.25:1), the mixture is stirred uniformly, then silver nitrate solution is dripped onto the Silicalite-1 molecular sieve (40 drops/min), equal volume impregnation is adopted, the mixture is stirred uniformly, the mixture is stirred in a 90 ℃ oven until the solvent volatilizes, then the temperature is raised to 110 ℃ for 13 hours, and the mixture is transferred to a muffle furnace for 2 hours at 450 ℃.
(3) Preparation of mixed catalysts
And uniformly mixing 1g of prepared lanthanum oxide carbonate and 4g of silver-loaded Silicalite-1 molecular sieve to prepare the catalyst LAG-cat-4.
Example 5
The preparation of the mixed catalyst LAG-cat-5 was carried out as in example 1, except that the weight ratio of the supported silver element to the molecular sieve was 0.01:1, and the weight ratio of lanthanum oxycarbonate to the silver-supported molecular sieve in the catalyst was 1:6.
Example 6
The preparation of the mixed catalyst LAG-cat-6 was carried out as in example 1, except that the weight ratio of the supported silver element to the molecular sieve was 0.3:1, and the weight ratio of lanthanum oxycarbonate to the silver-supported molecular sieve in the catalyst was 1:0.2.
Comparative example 1
The preparation of the mixed catalyst LAG-cat-D1 was carried out as in example 1, except that no silver was supported in the molecular sieve.
Test example 1
The catalyst prepared in the above examples and comparative examples, lanthanum oxycarbonate prepared in step (1) of example 1 and silver-loaded molecular sieve prepared in step (2) were tableted, sieved, 0.2g was weighed and charged into a fixed bed Inconel reactor, methane and oxygen were introduced at a molar ratio of 6:1 and a space velocity of 80000ml/gh at normal pressure, the reactor temperature was 550 ℃, and methane conversion, ethylene ethane and carbon two yields were as shown in Table 1.
Test example 2
The catalyst prepared in the above examples and comparative examples, lanthanum oxycarbonate prepared in step (1) of example 1 and silver-loaded molecular sieve prepared in step (2) were tableted, sieved, 0.2g was weighed and charged into a fixed bed Inconel reactor, methane and oxygen were introduced at a molar ratio of 6:1 under normal pressure, the space velocity of methane was 80000ml/gh, and the reactor bed temperature rise value due to exothermic reaction at the beginning of the oxidative coupling reaction of methane was designated as DeltaT in terms of ℃.
The results are shown in Table 1
TABLE 1
| Examples numbering | Methane conversion/% | Carbon Dihydrocarbon Selectivity/% | Yield of carbon diolefms/% | △T/℃ |
| Example 1 | 23.1 | 58.3 | 13.47 | 27 |
| Example 2 | 23.5 | 54.2 | 12.74 | 30 |
| Example 3 | 22.3 | 56.2 | 12.53 | 20 |
| Example 4 | 21.6 | 59.3 | 12.81 | 19 |
| Example 5 | 21.8 | 57.3 | 12.49 | 17 |
| Example 6 | 23.5 | 56.3 | 13.23 | 30 |
| Comparative example 1 | 22.8 | 53.5 | 12.20 | 33 |
| Lanthanum oxycarbonate | 23.5 | 52.2 | 12.27 | 42 |
| Silver-loaded molecular sieves | 15.2 | 60.3 | 9.17 | 12 |
As can be seen from the results in Table 1, the mixed catalyst provided by the invention can effectively reduce the temperature rise caused by bed heat release and reduce the damage of high temperature to the catalyst performance, thereby ensuring the catalytic effect. Within the preferred range of the present invention, the synergistic effect of the mixed catalyst can be further exerted.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. The mixed catalyst is characterized by comprising lanthanum oxide carbonate and a silver-loaded molecular sieve, wherein the weight ratio of the lanthanum oxide carbonate to the silver-loaded molecular sieve is 1:0.01-100;
wherein the molecular sieve is selected from one or more of TS-1, SBA-15, KIT-6, silicalite-1 and Silicalite-2; in the silver-loaded molecular sieve, the weight ratio of the load of silver element to the molecular sieve is 0.01-0.5:1.
2. The hybrid catalyst of claim 1, wherein the weight ratio of elemental silver loading to molecular sieve in the silver-loaded molecular sieve is from 0.025 to 0.25:1;
and/or in the mixed catalyst, the weight ratio of lanthanum oxide carbonate to silver-loaded molecular sieve is 1:0.2-8;
and/or the morphology of the lanthanum oxycarbonate is at least one selected from the group consisting of block, flake, flower, rod and needle;
and/or, the lanthanum oxycarbonate is nanoscale in at least one dimension.
3. The mixed catalyst according to claim 1 or 2, wherein the mixed catalyst is in a powder form or has at least one of a granular, hexagonal, hollow and plate form.
4. A method for preparing a hybrid catalyst, comprising: mixing lanthanum oxide and silver-loaded molecular sieve to obtain the mixed catalyst, wherein the weight ratio of lanthanum oxide to silver-loaded molecular sieve is 1:0.01-100;
wherein the molecular sieve is selected from one or more of TS-1, SBA-15, KIT-6, silicalite-1 and Silicalite-2; in the silver-loaded molecular sieve, the weight ratio of the load of silver element to the molecular sieve is 0.01-0.5:1.
5. The method of claim 4, wherein the weight ratio of elemental silver supported to molecular sieve in the silver-loaded molecular sieve is from 0.025 to 0.25:1;
and/or in the mixed catalyst, the weight ratio of lanthanum oxide carbonate to silver-loaded molecular sieve is 1:0.2-8;
and/or the morphology of the lanthanum oxycarbonate is at least one selected from the group consisting of block, flake, flower, rod and needle;
and/or, the lanthanum oxycarbonate is nanoscale in at least one dimension.
6. The method of claim 4 or 5, wherein the method of preparing the silver-loaded molecular sieve comprises: and dissolving a silver compound precursor, loading the silver compound precursor on a molecular sieve by an impregnation method, and sequentially carrying out first drying and first roasting on the obtained material to obtain the silver loaded molecular sieve.
7. The method according to claim 4 or 5, wherein the lanthanum oxycarbonate is obtained by a second calcination of lanthanum hydroxide or by a hydrothermal method using a water-soluble lanthanum salt as a starting material.
8. The method according to claim 4 or 5, wherein the lanthanum oxycarbonate is prepared by a process comprising:
dissolving water-soluble lanthanum salt in water, adding alkali liquor, continuously stirring for 3-10h after the mixed liquor is changed into milky gel, and then carrying out hydrothermal reaction on the obtained material;
and (3) sequentially centrifuging, washing, drying for the second time and roasting for the material subjected to the hydrothermal reaction to obtain nano lanthanum oxide carbonate.
9. The method according to claim 4 or 5, wherein the method further comprises: the lanthanum oxide and silver-loaded molecular sieve are mixed in a powdery form, or are mixed in a form of at least one of a granular form, a hexagonal form, a hollow form and a sheet form, or are mixed in a powdery form and are formed into at least one of a granular form, a hexagonal form, a hollow form and a sheet form.
10. A mixed catalyst prepared by the process of any one of claims 4-9.
11. Use of a mixed catalyst according to any one of claims 1-3 and 10 in a methane oxidative coupling reaction.
12. A process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with the mixed catalyst of any one of claims 1-3 and 10 in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, a mixed catalyst is prepared according to the method of any one of claims 4 to 9, and then methane is contacted with the resulting mixed catalyst in the presence of oxygen and under conditions of oxidative coupling of methane.
13. The method of claim 12, wherein the molar ratio of methane to oxygen is 2-10:1, a step of;
and/or, the contact temperature is 400-800 ℃;
and/or, the space velocity of methane is 5000-150000 mL/(g.h).
14. Use of a mixed catalyst according to any one of claims 1-3 and 10 for reducing the temperature rise caused by bed exotherm in a methane oxidative coupling reaction.
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| CN1458865A (en) * | 2000-09-18 | 2003-11-26 | 联合碳化化学及塑料技术公司 | Catalyst for oxidative dehydrogenation of hydrocarbons |
| CN1696084A (en) * | 2004-05-10 | 2005-11-16 | 中国科学院大连化学物理研究所 | Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon |
| CN103657640A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Load catalyst and preparation method and application thereof as well as method for preparing low carbon olefin by methane oxidative coupling |
| CN106140264A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of catalyst with lanthanum modified zsm-5 zeolite as carrier and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1458865A (en) * | 2000-09-18 | 2003-11-26 | 联合碳化化学及塑料技术公司 | Catalyst for oxidative dehydrogenation of hydrocarbons |
| CN1696084A (en) * | 2004-05-10 | 2005-11-16 | 中国科学院大连化学物理研究所 | Method for preparing C-2 hydrocarbon through catalyzing oxidative coupling of methane hydrocarbon |
| CN103657640A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Load catalyst and preparation method and application thereof as well as method for preparing low carbon olefin by methane oxidative coupling |
| CN106140264A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of catalyst with lanthanum modified zsm-5 zeolite as carrier and its preparation method and application |
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