CN113797913A - Magnesium-lanthanum composite oxide and preparation method and application thereof - Google Patents
Magnesium-lanthanum composite oxide and preparation method and application thereof Download PDFInfo
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- CN113797913A CN113797913A CN202010535500.0A CN202010535500A CN113797913A CN 113797913 A CN113797913 A CN 113797913A CN 202010535500 A CN202010535500 A CN 202010535500A CN 113797913 A CN113797913 A CN 113797913A
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- CN
- China
- Prior art keywords
- magnesium
- composite oxide
- lanthanum
- lanthanum composite
- methane
- Prior art date
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Links
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- RIAXXCZORHQTQD-UHFFFAOYSA-N lanthanum magnesium Chemical compound [Mg].[La] RIAXXCZORHQTQD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000011777 magnesium Substances 0.000 claims abstract description 33
- 239000011148 porous material Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- -1 alkali metal bicarbonate Chemical class 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 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 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical group 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- NNNSKJSUQWKSAM-UHFFFAOYSA-L magnesium;dichlorate Chemical compound [Mg+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NNNSKJSUQWKSAM-UHFFFAOYSA-L 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 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
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- 229910052799 carbon Inorganic materials 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
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- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
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- 239000001294 propane Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000013341 scale-up Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005049 combustion synthesis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
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- 238000004729 solvothermal method Methods 0.000 description 2
- 238000012990 sonochemical synthesis Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 238000004458 analytical method Methods 0.000 description 1
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- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
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- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/613—10-100 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention relates to the field of methane catalytic oxidation, and discloses a magnesium-lanthanum composite oxide, and a preparation method and application thereof. The molar ratio of Mg to La in the magnesium lanthanum composite oxide is 1: 0.02-1.2; wherein the XRD pattern of the magnesium lanthanum composite oxide has characteristic peaks at the positions of 23.05 +/-0.3, 25.83 +/-0.3, 26.01 +/-0.3, 27.45 +/-0.3, 31.02 +/-0.3, 33.74 +/-0.3, 43.26 +/-0.3, 45.02 +/-0.3, 46.3 +/-0.3, 47.75 +/-0.3, 50.86 +/-0.3, 56.3 +/-0.3, 57.75 +/-0.3, 58.01 +/-0.3, 64.1 +/-0.3, 8 +/-0.3, 71.5 +/-0.3, 3.2 +/-0.3 and 76 +/-0.3 of 2 theta. The magnesium-lanthanum composite oxide has larger pore volume, pore diameter and specific surface area, and is more favorable for generating active oxygen sites.
Description
Technical Field
The invention relates to the field of methane catalytic oxidation, in particular to a magnesium-lanthanum composite oxide and a preparation method and application thereof.
Background
One of the most basic raw materials in petrochemical industry. In the aspect of synthetic materials, the method is widely used for producing polyethylene, vinyl chloride and polyvinyl chloride, ethylbenzene, styrene and polystyrene, ethylene propylene rubber and the like; in the aspect of organic synthesis, the method is widely used for synthesizing ethanol, ethylene oxide, ethylene glycol, acetaldehyde, acetic acid, propionaldehyde, propionic acid and derivatives thereof and other basic organic synthesis raw materials; halogenated to prepare chloroethylene, chloroethane and bromoethane; alpha-olefin can be prepared by oligomerization, and then higher alcohol, alkylbenzene, etc. can be produced. In recent years, the discovery and exploitation of shale gas have revolutionized the development and utilization of natural gas. Therefore, the method for preparing ethane and ethylene by methane oxidative coupling, which is the most direct, effective and economically competitive natural gas utilization method, is increasingly receiving attention. Since the oxidative coupling reaction of methane is a strongly exothermic reaction and is carried out at high temperature, no industrial production is available so far, and therefore, the development of a methane oxidative coupling catalyst with excellent performance has practical significance.
In order to improve the reaction performance of the methane oxidative coupling catalyst, researchers have done much work, such as in CN103764276A, preparing a catalyst comprising: formula Ln14-xLn2xO6Wherein Ln1 and Ln2 are each independently a different lanthanide and x is a number greater than 0 to less than 4; and at least one doping element from groups 1-6, 8, 11, 13-15, or a combination thereof, wherein the doping element is present at a maximum concentration of 75 wt% of the catalyst; also contains doped metal elements: na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, Cs, S, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te or Mo. The catalyst, when used as a heterogeneous catalyst in oxidative coupling of methane at a temperature of 850 ℃ or less, 800 ℃ or less, for example 750 ℃ or less or 700 ℃ or less, has catalytic activity such that the hydrocarbon selectivity over carbon two is 50% or more and the methane conversion is 20% or more. CN101385982B mesoporous molecular sieve catalyst for preparing ethylene by methane oxidative coupling and its preparing process, wherein mesoporous molecular sieve is used as catalyst carrier to modify Na2WO4And Mn or Na2WO4And Mn, M (M ═ Li, Ce, Zr, La or Sr) and other catalytic active components are assembled in the pores of the mesoporous molecular sieve, so that the catalytic active components are highly isolated and dispersed, the activity and stability of the catalyst are improved, the preparation process of the catalyst is complex, and the preparation period is long. CN109569565A A preparation method and application of a non-stoichiometric defect fluorite catalyst for methane oxidative coupling adopts a defect structure to reduce the reaction temperature, and utilizes the traditional citric acid sol-gel preparation method to prepare the non-stoichiometric defect fluorite catalyst. The prepared catalyst has the problems of high catalytic activation 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 overcome the defects of low reaction activity, complex preparation process, long preparation period, high catalytic activation reaction temperature and difficult industrial application of a methane oxidative coupling catalyst in the prior art, and provides a magnesium-lanthanum composite oxide, a preparation method and application thereof, wherein the magnesium-lanthanum composite oxide has larger pore volume, pore diameter and specific surface area and is more beneficial to the generation of active oxygen sites; and the magnesium lanthanum composite oxide can ensure that the reaction for preparing the hydrocarbon above carbon by methane is carried out at a lower temperature (such as within the range of 400-450 ℃), reduces the requirements on a reactor and operating conditions, has higher methane conversion rate and higher hydrocarbon selectivity above carbon, and is more beneficial to industrial amplification production.
In order to achieve the above object, the present invention provides, in one aspect, a magnesium lanthanum composite oxide in which the molar ratio of Mg and La is 1:0.02 to 1.2; wherein the XRD pattern of the magnesium lanthanum composite oxide has characteristic peaks at the positions of 23.05 +/-0.3, 25.83 +/-0.3, 26.01 +/-0.3, 27.45 +/-0.3, 31.02 +/-0.3, 33.74 +/-0.3, 43.26 +/-0.3, 45.02 +/-0.3, 46.3 +/-0.3, 47.75 +/-0.3, 50.86 +/-0.3, 56.3 +/-0.3, 57.75 +/-0.3, 58.01 +/-0.3, 64.1 +/-0.3, 8 +/-0.3, 71.5 +/-0.3, 3.2 +/-0.3 and 76 +/-0.3 of 2 theta.
In the invention, the magnesium-lanthanum composite oxide is of a layered nano structure, has larger pore volume, pore diameter and specific surface area, and is beneficial to the generation of active oxygen sites, thereby promoting the progress of methane oxidative coupling reaction.
In a second aspect of the present invention, there is provided a method for producing a magnesium lanthanum composite oxide, the method comprising: in the presence of a solvent, mixing a magnesium precursor, a lanthanum precursor and a precipitator in a gradual contact mode, controlling the pH value of a mixed system in a range of 9-13 in the gradual contact mode, aging after the gradual contact is finished, separating a solid phase from an aged product, and sequentially drying and roasting.
In a third aspect of the invention, the compound is prepared by the method.
In a fourth aspect of the present invention, there is provided a process for producing a above-carbon hydrocarbon from methane, the process comprising: in the presence of oxygen, methane is contacted with the magnesium-lanthanum composite oxide for catalytic reaction; or preparing the magnesium-lanthanum composite oxide according to the method, and then contacting methane with the obtained magnesium-lanthanum composite oxide in the presence of oxygen to perform catalytic reaction.
The method for preparing the magnesium-lanthanum composite oxide provided by the invention is simple and environment-friendly, has short preparation period and low price of raw materials, and is easy for large-scale production and application.
The method for preparing the hydrocarbon above carbon by the methane has the advantages that the methane is contacted with the magnesium lanthanum composite oxide to carry out catalytic reaction in the presence of oxygen to prepare the hydrocarbon above carbon, the magnesium lanthanum composite oxide can ensure that the reaction for preparing the hydrocarbon above carbon by the methane can be carried out at lower temperature (such as the temperature range of 400-450 ℃), the requirements on a reactor and operation conditions are reduced, and the method has higher methane conversion rate and higher selectivity of the hydrocarbon above carbon, and is more beneficial to industrial amplification production.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the magnesium-lanthanum-magnesium-lanthanum composite oxide prepared by the method has larger pore volume, pore diameter and specific surface area, and is more favorable for generating active oxygen sites, thereby ensuring the excellent performance of the methane oxidation coupling catalyst.
(2) The magnesium lanthanum composite oxide provided by the invention shows good catalytic performance when used in methane oxidative coupling reaction, namely low catalytic activation reaction temperature, high methane conversion rate and high hydrocarbon selectivity over carbon, thereby being beneficial to industrial scale-up production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a magnesium lanthanum composite oxide obtained according to example 1;
fig. 2 is a TEM image of a transmission electron microscope of the magnesium lanthanum composite oxide obtained according to 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 magnesium-lanthanum composite oxide, wherein the molar ratio of Mg to La in the magnesium-lanthanum composite oxide is 1: 0.02-1.2; wherein the XRD pattern of the magnesium lanthanum composite oxide has characteristic peaks at the positions of 23.05 +/-0.3, 25.83 +/-0.3, 26.01 +/-0.3, 27.45 +/-0.3, 31.02 +/-0.3, 33.74 +/-0.3, 43.26 +/-0.3, 45.02 +/-0.3, 46.3 +/-0.3, 47.75 +/-0.3, 50.86 +/-0.3, 56.3 +/-0.3, 57.75 +/-0.3, 58.01 +/-0.3, 64.1 +/-0.3, 8 +/-0.3, 71.5 +/-0.3, 3.2 +/-0.3 and 76 +/-0.3 of 2 theta.
In the present invention, it is preferable that the molar ratio of Mg and La in the magnesium lanthanum composite oxide is 1:0.05 to 0.1.
In the present invention, preferably, the magnesium lanthanum composite oxide is a layered nanostructure.
In the invention, the specific surface area, the pore volume and the pore diameter of the magnesium lanthanum composite oxide can be measured according to a nitrogen adsorption method, the specific surface area is calculated by adopting a BET method, and the pore volume is calculated by adopting a BJH model. The specific surface area of the magnesium lanthanum composite oxide is preferably 40 to 500m2A/g, more preferably 50 to 200m2(ii) in terms of/g. The pore volume of the magnesium lanthanum composite oxide is preferably 0.1-0.5cm3In terms of/g, more preferably 0.2-0.4cm3(ii) in terms of/g. The average pore diameter of the magnesium lanthanum composite oxide is preferably 8 to 20nm, more preferably 10 to 15 nm.
In the present invention, in order to further reduce the temperature of the catalytic activation reaction and increase the conversion rate of methane, the magnesium-lanthanum composite oxide may further include other metal elements, and the other metal elements are preferably at least one selected from Li, Na, Ca, Cs, Ce, W, Mn, Ru, Rh, Ni, and Pt. The method of supporting other metals on the above-mentioned magnesium lanthanum composite oxide is not particularly limited in the present invention, and those skilled in the art can perform the methods in the prior art, for example: mixing, precipitation/co-precipitation, impregnation, sol-gel, template/surface derived metal oxide synthesis, solid state synthesis of mixed metal oxides, micro-emulsion techniques, solvothermal synthesis, sonochemical synthesis or combustion synthesis, etc., to achieve doping of other metals.
In the present invention, it is preferable that the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 0.01 to 50 wt%, for example, 0.01 wt%, 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, or any value between the above values. More preferably 0.1 to 20 wt%, e.g., 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt% or any value therebetween. Further preferably 1 to 5 wt%, e.g., 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or any value therebetween.
In the present invention, the other metal elements are present in the form of oxides.
At a reaction pressure of 0.004MPa, methane: the molar ratio of oxygen is 5: 1. the reaction activation temperature of the magnesium lanthanum composite oxide of the present invention is preferably 500 ℃ or lower, more preferably 455 ℃ or lower, and further preferably 400-450 ℃ under reaction conditions in which the space velocity of methane is 40000 mL/(g.h) and the reaction time is 100 h. The "reaction activation temperature" refers to the temperature of the catalyst bed at which any one of hydrocarbons including carbon two is formed in the reaction product as detected by gas chromatography.
In a second aspect of the present invention, there is provided a method for producing a magnesium lanthanum composite oxide, the method comprising: in the presence of a solvent, mixing a magnesium precursor, a lanthanum precursor and a precipitator in a gradual contact mode, controlling the pH value of a mixed system in a range of 9-13 in the gradual contact mode, aging after the gradual contact is finished, separating a solid phase from an aged product, and sequentially drying and roasting.
In the invention, the step-by-step contact mode can be adopted for mixing, and the step-by-step contact mode is as follows: preparing a precipitant solution in advance to enable the pH value of the precipitant solution to be 12-13, and mixing a magnesium precursor and a lanthanum precursor with the precipitant solution in a gradual contact manner. According to a preferred embodiment of the present invention, a magnesium precursor and a lanthanum precursor are dissolved in a solvent to form a solution a, a precipitant is dissolved in the solvent to form a solution B, the solution B is added dropwise to water until the pH of the formed solution is 12 to 13, the solution a is added dropwise until the pH of the formed mixed solution is 10 to 11, then the dropping speeds of the solution a and the solution B are controlled so that the pH of the formed mixed system is controlled within a range of 9 to 11 until the solution a and the solution B are completely dropped, then aging is performed, a solid phase is separated from the aged product, and drying and baking are sequentially performed. Specifically, in the solution A, the weight concentration of magnesium element is as follows: 1-3 wt%, and the weight concentration of lanthanum element is as follows: 1-6 wt%; in the B solution, the weight concentration of carbon elements is as follows: 1-3 wt%; in a mixed system formed after the solution A and the solution B are completely dripped, the weight concentration of the magnesium element is as follows: 0.5-1.1 wt%, and the weight concentration of lanthanum element is as follows: 0.4-2 wt%, and the weight concentration of carbon element is: 0.5-1.2 wt%.
In the present invention, the solvent may be water, and preferably, the water is deionized water.
In the present invention, the precipitant may be a substance whose solution is alkaline (preferably, pH 9 to 13) after hydrolysis, and preferably, the precipitant is an alkali metal carbonate and/or an alkali metal bicarbonate. The carbonate of the alkali metal is water-soluble carbonate of the alkali metal, and sodium carbonate and/or potassium carbonate are/is more preferable; and/or the alkali metal bicarbonate is an alkali metal water soluble bicarbonate, more preferably sodium bicarbonate and/or potassium bicarbonate. Further preferably, the precipitant may contain a water-soluble base to ensure an alkaline environment required for the coprecipitation reaction, and still further preferably, the water-soluble base is sodium hydroxide and/or potassium hydroxide.
In the present invention, preferably, the magnesium precursor is a water-soluble magnesium salt, more preferably at least one selected from the group consisting of magnesium nitrate, magnesium chloride and magnesium chlorate, and further preferably magnesium nitrate; and/or the lanthanum precursor is a water-soluble lanthanum salt, more preferably lanthanum nitrate and/or lanthanum acetate, and further preferably lanthanum nitrate.
In the present invention, preferably, the molar ratio of the magnesium precursor in Mg to the lanthanum precursor in La is 1: 0.01 to 1, more preferably 1: 0.2-0.4.
In the present invention, the amount of the magnesium precursor is preferably 0.1 to 50g, preferably 1 to 20g, more preferably 1 to 5g, in terms of Mg, per 100g of the mixed system.
In the invention, in order to promote the coprecipitation reaction, the aging temperature is 50-70 ℃; the aging time is 10 to 50 hours, preferably 12 to 36 hours.
In the present invention, preferably, the precipitant is used in an amount such that the precipitant provides carbonate and/or bicarbonate in a molar ratio of 1 to 5: 1.
in the invention, in order to promote the generation of the magnesium lanthanum composite oxide, the roasting temperature is preferably 500-750 ℃, and more preferably 550-600 ℃; the time for the calcination is preferably 2 to 10 hours, more preferably 2 to 8 hours, and still more preferably 2 to 5 hours.
In the present invention, the drying method is not particularly limited, and a method of drying in the air or in a drying apparatus may be used.
In the present invention, the method may further comprise a step of washing. The manner of washing is not particularly limited, and washing with water (preferably deionized water) may be carried out 2 to 5 times.
In the invention, in order to further reduce the temperature of the catalytic activation reaction and improve the conversion rate of methane, the method further comprises loading other metal elements on the roasted product, wherein the other metal elements are selected from at least one of Li, Na, Ca, Cs, Ce, W, Mn, Ru, Rh, Ni and Pt. The method of supporting other metals on the above-mentioned magnesium lanthanum composite oxide is not particularly limited in the present invention, and those skilled in the art can perform the methods in the prior art, for example: mixing, precipitation/co-precipitation, impregnation, sol-gel, template/surface derived metal oxide synthesis, solid state synthesis of mixed metal oxides, micro-emulsion techniques, solvothermal synthesis, sonochemical synthesis, combustion synthesis, etc., to achieve doping of other metals.
According to a preferred embodiment of the invention, other elements are doped in an impregnation mode, and after the impregnation is finished, the magnesium-lanthanum composite oxide is obtained through drying and roasting in sequence, wherein the drying temperature is 80-120 ℃ and the drying time is 10-25 hours. The roasting temperature is 500-750 ℃, and the roasting time is 3-5 h.
The amount of the other metal element is not limited in the present invention as long as the weight percentage of the other metal element in the magnesium lanthanum composite oxide can be made 0.01 to 50 wt%, for example, 0.01 wt%, 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt% or any value therebetween; more preferably 0.1 to 20 wt%, e.g., 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, or any value therebetween; further preferably 1 to 5 wt%, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or any value between the above values.
In the present invention, the method may further include a step of molding the obtained magnesium lanthanum composite oxide. The forming method is not limited, and conventional extrusion forming can be adopted, and the obtained formed composite carrier can be cylindrical, honeycomb or sheet. And then crushing and screening the formed composite carrier, wherein the particle size of the obtained composite carrier is 40-60 meshes.
In a third aspect of the invention, the compound is prepared by the method.
In a fourth aspect of the present invention, there is provided a process for producing a above-carbon hydrocarbon from methane, the process comprising: in the presence of oxygen, methane is contacted with the magnesium-lanthanum composite oxide for catalytic reaction; or preparing the magnesium-lanthanum composite oxide according to the method, and then contacting methane with the obtained magnesium-lanthanum composite oxide 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. Specifically, the magnesium lanthanum composite oxide 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 the invention, in order to promote the catalytic reaction and improve the conversion rate of methane, the molar ratio of the consumption of the methane to the consumption of the oxygen is 2-10: 1, preferably 3-8: 1.
In the present invention, the conditions of the catalytic reaction are not particularly limited and may be conventionally selected in the art, and preferably, the reaction activation temperature of the catalytic reaction is 400-450 ℃. The time of the catalytic reaction is 1-500 h. The pressure of the catalytic reaction is 0.004-0.02 MPa. The space velocity of methane is 1000-80000 mL/(g.h), preferably 10000-50000 mL/(g.h).
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 above-mentioned hydrocarbon containing carbon two or more may be ethane, ethylene, propylene, propane, butene, butane and a small amount of higher hydrocarbons.
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. Room temperature means "25 ℃ C" pressure means gauge pressure. 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. The pH value during the experiment was measured using Mettler S220.
Example 1
26.05g Mg (NO)3)2·6H2O and 14.66g La (NO)3)3·6H2O in 95g of deionized water, denoted as solution (A), K2CO3(40.3g) and NaOH (11.7g) were dissolved in deionized water (180g) and was noted as solution (B). 60g of deionized water was added to the flask, and then the solution (B) was added dropwise to the deionized water until the pH of the solution reached 13, at which time dropwise addition of the solution (A) was started until the pH of the solution reached 10. Controlling the flow rates of (A) and (B) willThe pH of the solution was maintained at 10. + -. 0.5 until all the addition of the metal ion solution (A) was complete. The resulting slurry/mixture was aged at 65 ℃ for 12 hours. The precipitate was then isolated by filtration and washed 3 times with deionized water (volume ═ 1.5L) at 70 ℃. The resulting solid was dried in an oven at 80 ℃ for 24 h. Roasting at 500 deg.c in air for 5 hr. Cooling to room temperature, tabletting, crushing, sieving and taking the part of 40-60 meshes to obtain the magnesium-lanthanum composite oxide.
Example 2
42.7g of MgCl2·6H2O and 2.21g La (CH)3COO)3Dissolved in 100g of deionized water, denoted as solution (A), KHCO is added3(50g) And NaOH (10.1g) was dissolved in deionized water (200g) and was noted as solution (B). 40g of deionized water was added to the flask, and then the solution (B) was added dropwise to the deionized water until the pH of the solution reached 12, at which time dropwise addition of the solution (A) was started until the pH of the solution reached 9.5. The flow rates of (A) and (B) were controlled to maintain the pH of the solution at 10.5. + -. 0.5 until all metal ion solution (A) addition was complete. The resulting slurry/mixture was aged at 50 ℃ for 24 hours. The precipitate was then isolated by filtration and washed 3 times with deionized water (volume ═ 1.5L) at 70 ℃. The resulting solid was dried in an oven at 80 ℃ for 24 h. Roasting at 600 ℃ in air for 2 h. Cooling to room temperature, tabletting, crushing, sieving and taking the part of 40-60 meshes to obtain the magnesium-lanthanum composite oxide.
Example 3
A magnesium lanthanum composite oxide was prepared by the method of example 1, except that Mg (NO)3)2·6H2Mass of O26.05 g and La (NO)3)3·6H2The mass of O was 43.3 g.
Example 4
A magnesium lanthanum composite oxide was prepared by the method of example 1, except that Mg (NO)3)2·6H2Mass of O26.05 g and La (NO)3)3·6H2The mass of O was 4.5 g.
Example 5
A magnesium lanthanum composite oxide was prepared according to the method of example 1, except that 2g of the solid was calcined and added to a cerium nitrate solution, the composition of the solution being 0.062g of cerium nitrate dissolved in 50g of deionized water, cerium was supported by impregnation, stirred in a water bath at 80 ℃ until water was volatilized, dried at 120 ℃ for 24 hours, and then calcined in a muffle furnace at 550 ℃ for 4 hours. Cooling to room temperature, tabletting, crushing, sieving and taking the part of 40-60 meshes to obtain the magnesium-lanthanum composite oxide.
Example 6
The magnesium lanthanum composite oxide was prepared according to the method of example 1, except that 2g of the solid was calcined and added to a strontium nitrate solution, the solution composition was such that 0.060g of strontium nitrate was dissolved in 50g of deionized water, strontium was loaded by the impregnation method, stirred in a water bath at 80 ℃ until the water was volatilized, dried at 120 ℃ for 12 hours, and then placed in a muffle furnace for calcination at 550 ℃ for 4 hours. Cooling to room temperature, tabletting, crushing, sieving and taking the part of 40-60 meshes to obtain the magnesium-lanthanum composite oxide.
Example 7
A magnesium lanthanum composite oxide was prepared according to the method of example 2, except that the calcination temperature was 750 ℃ and the calcination time was 8 hours in the preparation process.
Comparative example 1
A magnesium lanthanum composite oxide was prepared according to the method of example 1, except that the mixing process of the solutions was not controlled by pH during the preparation process, but the two solutions were directly mixed.
Comparative example 2
A magnesium lanthanum composite oxide was prepared by the method of example 1, except that Mg (NO) was added3)2·6H2Substitution of O for equimolar Ba (NO)3)2La (NO)3)3·6H2Substitution of O for equimolar Ce (NO)3)3·6H2O。
Test example 1
The nitrogen adsorption and desorption experiments of the composite oxide samples obtained in the examples and comparative examples were carried out on a fully automatic physicochemical 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 2
0.2g of the composite oxides obtained in examples and comparative examples were charged in a fixed bed quartz reactor respectively for oxidative coupling of methane to ethylene ethane at a reaction pressure of 0.004MPa, methane: the molar ratio of oxygen is 5: 1, the contact time is 100h, the space velocity of methane is 20000 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%
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%
The yield of hydrocarbons over carbon two, i.e., ethane selectivity, ethylene selectivity, propylene selectivity, propane selectivity, hydrocarbon over carbon two, i.e., methane conversion rate × hydrocarbon over carbon two
The results obtained are shown in table 1.
Test example 3
The composite oxides obtained in the examples and comparative examples were subjected to X-ray powder diffractometry using a Bruker D8 Adti diffractometerThe upper part is carried out by adopting a copper target with characteristic spectrum wavelength
The XRD patterns of the magnesium lanthanum composite oxides obtained in examples 1 to 7 have characteristic peaks at 23.05, 25.83, 26.01, 27.45, 31.02, 33.74, 43.26, 45.02, 46.3, 47.75, 50.86, 56.3, 57.75, 58.01, 64.1, 8.0, 71.5, 3.2 and 76 in 2 theta. Wherein the X-ray diffraction pattern obtained in example 1 is shown in FIG. 1.
Test example 4
The magnesium lanthanum composite oxide obtained in the examples was subjected to a transmission electron microscope test using a test instrument model JEOL 2100F-FEG with an acceleration voltage of 200 kV. The test result shows that the magnesium-lanthanum composite oxide obtained in the embodiment is of a layered nano structure. The TEM image of the transmission electron microscope obtained in example 1 is shown in FIG. 2.
Test example 5
The reaction activation temperature is the temperature at which the oxidative coupling of methane starts to occur, i.e., the temperature of the catalyst bed at which the formation of any hydrocarbon other than carbon dioxide in the reaction product is detected. The reaction activation temperatures of the composite oxides of examples and comparative examples were measured by thermocouple monitoring of the temperature at the point of contact of the reaction mass with the bed, and the reaction products were detected at a series of temperatures of 350 deg.C, 360 deg.C, 370 deg.C, 380 deg.C, 386 deg.C, 400 deg.C, 410 deg.C, 413 deg.C, 415 deg.C, 418 deg.C, 420 deg.C, 425 deg.C, 430 deg.C, 433 deg.C, 435 deg.C, 438 deg.C, 440 deg.C, 442 deg.C, 444 deg.C, 446 deg.C, 448 deg.C, 450 deg.C, 452 deg.C, 455 deg.C and 480 deg.C, respectively, and other conditions were the same as in test example 2.
Test example 6
The element contents of the composite oxides in examples and comparative examples were measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES) having an instrument model of a fisher iCAP 6500 analyzer, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, when the composite oxides obtained in examples 1 to 7 and comparative examples 1 to 2 were used in the oxidative coupling reaction of methane, the reaction activation temperatures of examples 1 to 7 were all 450 ℃ or lower, and after 100 hours of reaction, high methane conversion and hydrocarbon selectivity over carbon were still maintained; the reaction activation temperatures of comparative examples 1 to 2 were 650 ℃ and 700 ℃ respectively, and after 100 hours of reaction, the methane conversion rate, the selectivity to carbon dioxide, and the yield to carbon dioxide were all reduced compared to examples 1 to 7, indicating that the magnesium lanthanum composite oxide of the present invention has a lower reaction activation temperature, and also has excellent stability, which is advantageous for industrial scale-up production. Further, examples 1 and 4, in which the molar ratio of Mg and La falls within the preferred range of the present invention, are superior in catalytic effect to examples 2 and 3, and it is demonstrated that superior technical effect can be obtained by controlling the molar ratio of Mg and La within the preferred range.
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 (16)
1. The magnesium lanthanum composite oxide is characterized in that the molar ratio of Mg to La in the magnesium lanthanum composite oxide is 1: 0.02-1.2; wherein the XRD pattern of the magnesium lanthanum composite oxide has characteristic peaks at the positions of 23.05 +/-0.3, 25.83 +/-0.3, 26.01 +/-0.3, 27.45 +/-0.3, 31.02 +/-0.3, 33.74 +/-0.3, 43.26 +/-0.3, 45.02 +/-0.3, 46.3 +/-0.3, 47.75 +/-0.3, 50.86 +/-0.3, 56.3 +/-0.3, 57.75 +/-0.3, 58.01 +/-0.3, 64.1 +/-0.3, 8 +/-0.3, 71.5 +/-0.3, 3.2 +/-0.3 and 76 +/-0.3 of 2 theta.
2. The magnesium lanthanum composite oxide according to claim 1, characterized in that the magnesium lanthanum composite oxide is a layered nanostructure;
and/or the specific surface area of the magnesium-lanthanum composite oxide is 40-500m2A/g, preferably from 50 to 200m2/g；
And/or the pore volume of the magnesium-lanthanum composite oxide is 0.1-0.5cm3In g, preferably from 0.2 to 0.4cm3/g；
And/or the average pore diameter of the magnesium-lanthanum composite oxide is 8-20nm, preferably 10-15 nm;
preferably, the molar ratio of Mg to La in the magnesium lanthanum composite oxide is 1: 0.05-0.1.
3. The magnesium lanthanum composite oxide according to claim 1 or 2, characterized in that the magnesium lanthanum composite oxide further comprises other metal elements selected from at least one of Li, Na, Ca, Cs, Ce, W, Mn, Ru, Rh, Ni, and Pt;
preferably, the weight percentage of the other metal elements in the magnesium lanthanum composite oxide is 0.01 to 50 wt%, more preferably 0.1 to 20 wt%, and still more preferably 1 to 5 wt%.
4. A method for producing a magnesium lanthanum composite oxide, characterized by comprising: in the presence of a solvent, mixing a magnesium precursor, a lanthanum precursor and a precipitator in a gradual contact mode, controlling the pH value of a mixed system in a range of 9-13 in the gradual contact mode, aging after the gradual contact is finished, separating a solid phase from an aged product, and sequentially drying and roasting.
5. The method of claim 4, wherein the stepwise contacting is by: preparing a precipitant solution in advance to enable the pH value of the precipitant solution to be 12-13, and mixing a magnesium precursor and a lanthanum precursor with the precipitant solution in a gradual contact manner.
6. The method according to claim 4 or 5, characterized in that the molar ratio of the magnesium precursor, expressed as Mg, to the lanthanum precursor, expressed as La, is 1: 0.01-1, preferably 1: 0.2-0.4.
7. The method according to claim 6, wherein the magnesium precursor is a water-soluble magnesium salt, preferably at least one selected from the group consisting of magnesium nitrate, magnesium chloride and magnesium chlorate, more preferably magnesium nitrate;
and/or the lanthanum precursor is water-soluble lanthanum salt, preferably lanthanum nitrate and/or lanthanum acetate, and more preferably lanthanum nitrate;
and/or the solvent is water, preferably the water is deionized water.
8. A process according to claim 4 or 5, characterized in that the precipitant is an alkali metal carbonate and/or an alkali metal bicarbonate; the carbonate of the alkali metal is water-soluble carbonate of the alkali metal, and preferably sodium carbonate and/or potassium carbonate; and/or the alkali metal bicarbonate is an alkali metal water-soluble bicarbonate, preferably sodium bicarbonate and/or potassium bicarbonate.
9. A method according to claim 8, characterized in that the amount of said precipitating agent is such that the molar ratio of carbonate and/or bicarbonate provided by said precipitating agent to said magnesium precursor, calculated as Mg, is from 1 to 5: 1.
10. the process according to claim 9, characterized in that the amount of the magnesium precursor, expressed as Mg, is 0.1 to 50g, preferably 1 to 20g, more preferably 1 to 5g, per 100g of the mixed system.
11. The method according to claim 4 or 5, further comprising supporting other metal elements selected from at least one of Li, Na, Ca, Cs, Ce, W, Mn, Ru, Rh, Ni, and Pt on the calcined product;
and/or, the other metal element is used in an amount such that the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 0.01 to 50 wt%, more preferably 0.1 to 20 wt%, and still more preferably 1 to 5 wt%.
12. The method as claimed in claim 11, wherein the roasting temperature is 500-750 ℃, preferably 550-600 ℃; the roasting time is 2-10h, preferably 2-8h, and more preferably 2-5 h.
13. The method according to claim 4 or 5, wherein the temperature of the aging is 50-70 ℃; the time is 10 to 50 hours, preferably 12 to 36 hours.
14. A magnesium lanthanum composite oxide, characterized in that it is prepared by the method of any one of claims 4 to 13.
15. A method for producing a hydrocarbon containing more than two carbon atoms from methane, the method comprising: contacting methane with the magnesium lanthanum composite oxide according to any one of claims 1 to 3 and claim 14 in the presence of oxygen to perform a catalytic reaction;
or preparing a magnesium lanthanum composite oxide according to the method of any one of claims 4 to 13, and then contacting methane with the obtained magnesium lanthanum composite oxide in the presence of oxygen to perform a catalytic reaction.
16. The method according to claim 15, wherein the molar ratio of the methane and the oxygen is 2-10: 1, preferably 3-8: 1;
preferably, the reaction activation temperature of the catalytic reaction is 400-450 ℃; the time of the catalytic reaction is 1-500 h; the pressure of the catalytic reaction is 0.004-0.02MPa, and the space velocity of the methane is 1000-.
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