CN115106122B - Preparation method and application of molecular sieve catalyst - Google Patents
Preparation method and application of molecular sieve catalyst Download PDFInfo
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- CN115106122B CN115106122B CN202110309379.4A CN202110309379A CN115106122B CN 115106122 B CN115106122 B CN 115106122B CN 202110309379 A CN202110309379 A CN 202110309379A CN 115106122 B CN115106122 B CN 115106122B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 42
- 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 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 compounds dimethyl ether Chemical class 0.000 claims abstract description 8
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 74
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 55
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 32
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 23
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 10
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 48
- 238000005810 carbonylation reaction Methods 0.000 abstract description 32
- 230000006315 carbonylation Effects 0.000 abstract description 28
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 34
- 239000007789 gas Substances 0.000 description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 229940050176 methyl chloride Drugs 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- UXKIPTJTWDKGSX-UHFFFAOYSA-N CCl.[C] Chemical compound CCl.[C] UXKIPTJTWDKGSX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QOTAEASRCGCJDN-UHFFFAOYSA-N [C].CO Chemical compound [C].CO QOTAEASRCGCJDN-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- QECJIGNJADOMIG-UHFFFAOYSA-N [C].COC Chemical compound [C].COC QECJIGNJADOMIG-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- FSTGPONFPZSUQS-UHFFFAOYSA-N [C].C(C)(=O)OC Chemical compound [C].C(C)(=O)OC FSTGPONFPZSUQS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Abstract
The application discloses a preparation method and application of a molecular sieve catalyst, wherein the method comprises the following steps: (1) Heating a material containing a mordenite molecular sieve and an organic alkali source to obtain an intermediate product; (2) And roasting the intermediate product to obtain the molecular sieve catalyst. The catalyst prepared by the application is used for the carbonylation of small molecular compounds dimethyl ether, methanol or halogenated methane, and has high activity and stable performance.
Description
Technical Field
The application relates to a preparation method and application of a molecular sieve catalyst, and belongs to the field of catalysis.
Background
The urgent desire for continuous growth of energy demand and improvement of environmental quality makes the development of energy resources in China face unprecedented challenges. Based on the energy safety requirement and the energy structure characteristics of rich coal, lean oil and less gas in China, the efficient conversion and clean utilization of energy are necessary choices for the energy development in China. Small molecule compounds such as methanol, dimethyl ether and methyl halide are important platform compounds that can be based on carbon dioxide, natural gas as raw materials. The directional conversion of small molecular compounds to prepare high added value compounds such as low-carbon olefins, gasoline, aromatic hydrocarbons, paraxylene and oxygen-containing compounds such as acetic acid, methyl acetate, ethanol and the like is an effective way for energy efficient and clean utilization.
The directional synthesis of C2 compound-acetic acid and methyl acetate by the carbonylation of small molecular compounds (methanol, dimethyl ether and halogenated methane) and CO is one of important research directions of C1 chemical conversion, and has extremely important application background and good market prospect. MOR, FER and OFF having an eight-membered ring channel structure are catalytically active for ether carbonylation, wherein a space time yield of 0.163-MeOAc (g-Cat. H) -1 is obtained at a reaction pressure of 1MPa and a temperature of 165℃with mordenite as a catalyst. After the metal Cu and Ag are introduced on the MOR catalyst, the carbonylation performance of the MOR catalyst under the reaction condition (hydrogen atmosphere, 250-300 ℃) is better than that of an unmodified MOR sample. Pyridine organic amine pre-adsorption is utilized to improve the property of mordenite, and because pyridine substances only can adsorb acid sites in a toxic twelve-membered ring pore canal due to size limitation, carbon deposition generation is inhibited to improve the carbonylation stability of the catalyst, so that the activity of the catalyst is kept stable within 48 hours of reaction. The silicon tetrachloride vapor modified mordenite molecular sieve catalyst can greatly improve the stability of the catalyst in dimethyl ether carbonylation by selectively removing skeleton aluminum sites in a 12-membered ring pore canal. An in-situ synthesis method for regulating and controlling acid center drop and distribution of mordenite, and a mordenite molecular sieve catalyst with excellent dimethyl ether carbonylation activity is successfully prepared by regulating and controlling the acid center drop. The foregoing has been directed primarily to the investigation of mordenite catalyzed carbonylation of dimethyl ether. The development of the catalyst is not only applicable to the dimethyl ether carbonylation reaction, but also applicable to the research of the development of the catalyst for the methanol and halogenated methane carbonylation reaction, and has important application value.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a molecular sieve catalyst, which comprises the steps of mixing a mordenite molecular sieve with an organic base, heating and roasting to obtain the molecular sieve catalyst. The method is simple and convenient, and has strong operability. Can realize the regulation and control of the acid position of the molecular sieve catalyst, so that the catalyst has higher activity and target product selectivity.
According to one aspect of the present invention, there is provided a method of preparing a molecular sieve catalyst, the method comprising: (1) Heating a material containing a mordenite molecular sieve and an organic alkali source to obtain an intermediate product; (2) And roasting the intermediate product to obtain the molecular sieve catalyst.
Optionally, the organic base is selected from organic amines; the organic amine is at least one selected from a monobasic organic amine, a dibasic organic amine and a tribasic organic amine.
Optionally, the mono-organic amine is selected from at least one of compounds having a chemical formula shown in formula I:
Wherein R 1,R2,R3 is independently selected from any one of the alkyl groups of H, C 1～C10; r 1,R2,R3 cannot be H at the same time.
Alternatively, in formula I, R 1,R2,R3 is independently selected from any one of the alkyl groups of H, C 1～C7; r 1,R2,R3 cannot be H at the same time.
Alternatively, in formula I, R 1,R2,R3 is independently selected from any one of H、CH3-、CH3CH2-、CH3CH2CH2-、CH3(CH2)2CH2-、CH3(CH2)3CH2-、CH3(CH2)4CH2-、CH3(CH2)5CH2-、(CH3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3)CH-.
Alternatively, in formula I, R 1,R2,R3 is independently selected from one of H、CH3、CH3CH2-、CH3CH2CH2-、CH3(CH2)2CH2-.
Alternatively, in formula I, R 1,R2,R3 is independently selected from one of H, CH 3、CH3CH2 -.
Alternatively, R 1,R2,R3 are the same, but different are H.
Alternatively, R 1,R2,R3 are not the same.
Preferably, the monobasic organic amine is selected from at least one of triethylamine and n-butylamine.
Preferably, the dibasic organic amine is selected from diethylamine.
Alternatively, the mono-organic amine is selected from alkyl ammonium hydroxides; the alkyl ammonium hydroxide is selected from at least one of compounds having a chemical formula shown in formula II:
Wherein R 4,R5,R6,R7 is independently selected from any one of the alkyl groups of C 1～C10.
Alternatively, in formula II, R 4,R5,R6,R7 is independently selected from any one of the alkyl groups of C 1～C7.
Alternatively, in formula II, R 4,R5,R6,R7 is independently selected from any one of CH3-、CH3CH2-、CH3CH2CH2-、CH3(CH2)2CH2-、CH3(CH2)3CH2-、CH3(CH2)4CH2-、CH3(CH2)5CH2-、(CH3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3)CH-.
Alternatively, in formula II, R 4,R5,R6,R7 is independently selected from one of CH3-、CH3CH2-、CH3CH2CH2-CH3(CH2)2CH2-、CH3(CH2)3CH2-、CH3(CH2)4CH2-、CH3(CH2)5CH2-.
Alternatively, R 4,R5,R6,R7 is different.
Alternatively, R 4,R5,R6,R7 is the same.
Preferably, the alkylammonium hydroxide is at least one selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide.
Optionally, the preparation method comprises the following steps: (1) Mixing the mordenite molecular sieve with an organic alkali source, and heating under a closed condition to obtain an intermediate; (2) And roasting the intermediate to obtain the molecular sieve catalyst.
Optionally, the heating conditions are: the temperature is 50-220 ℃ and the time is 5-100 hours.
Optionally, the upper temperature limit of the heating is selected from 60 ℃, 70 ℃,80 ℃,90 ℃, 100 ℃, 120 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃,200 ℃, 210 ℃ or 220 ℃; the lower limit is selected from 50 ℃, 60 ℃, 70 ℃,80 ℃,90 ℃, 100 ℃, 120 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃,200 ℃ or 210 ℃.
Optionally, the upper time limit of heating is selected from 6 hours, 12 hours, 18 hours, 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, 80 hours, 90 hours, or 100 hours; the lower limit is selected from 5 hours, 6 hours, 12 hours, 18 hours, 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, 80 hours, 90 hours or 99 hours.
Optionally, in step (1), the mordenite molecular sieve is mixed with an organic alkali source and treated in a closed reaction vessel at a temperature of 50 to 220 ℃ for 5 to 100 hours.
Optionally, the heating conditions are: the temperature is 80-200 ℃ and the time is 12-72 hours.
Preferably, the heating conditions are: the temperature is 100-200 ℃ and the time is 18-60 hours.
Optionally, the firing conditions are: the temperature is 450-650 ℃ and the time is 1.5-10 hours.
Optionally, the upper temperature limit of the roasting is 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃ or 650 ℃; the lower limit is selected from 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃ or 600 ℃.
Optionally, the upper time limit of the firing is selected from 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, or 10 hours; the lower limit is selected from 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, or 9.5 hours.
Optionally, the firing conditions are: the temperature is 450-600 ℃ and the time is 2-8 hours.
Optionally, the firing conditions are: the temperature is 450-550 ℃ and the time is 3-7 hours.
Preferably, the conditions of the calcination are: the temperature is 500-580 ℃ and the time is 3-6 hours.
Optionally, the mordenite molecular sieve has a silicon to aluminum atomic ratio of: si/al=6 to 50.
Optionally, the upper limit of the silicon to aluminum atomic ratio of the mordenite molecular sieve is selected from 8, 10, 15, 20, 25, 30, 35, 40, 50; the lower limit is selected from 6, 8, 10, 15, 20, 25, 30, 35, 40 or 49.
Optionally, the mordenite molecular sieve is selected from at least one of Na-MOR, NH 4 -MOR, H-MOR molecular sieves.
Optionally, the organic alkali source further comprises a solvent; the solvent is selected from water.
Optionally, the mass content of the organic alkali in the organic alkali solution is 0.5% -99.9%.
Optionally, the upper limit of the mass content of the organic base in the organic base solution is selected from 0.8%, 1.0%, 1.5%, 2.0%, 5.0%, 10.0%, 20.0%, 25.0%, 30.0%, 40.0%, 50.0%, 60.0%, 70.0%, 75.0%, 80.0%, 90.0% or 99.9%; the lower limit is selected from 0.5%, 0.8%, 1.0%, 1.5%, 2.0%, 5.0%, 10.0%, 20.0%, 25.0%, 30.0%, 40.0%, 50.0%, 60.0%, 70.0%, 75.0%, 80.0% or 90.0%.
Optionally, the ratio of the mordenite molecular sieve to the organic alkali source is 1g:2 ml-1 g:20ml.
Optionally, the upper limit of the ratio of the added amounts of the mordenite molecular sieve and the organic alkali source is selected from 1g:4ml, 1g:6ml, 1g:8ml, 1g:10ml, 1g:12ml, 1g:14ml, 1g:15ml, 1g:16ml, 1g:18ml or 1g:2ml; the lower limit is selected from 1g:2ml, 1g:4ml, 1g:6ml, 1g:8ml, 1g:10ml, 1g:12ml, 1g:14ml, 1g:15ml, 1g:16ml or 1g:18ml.
According to another aspect of the present application, there is provided a molecular sieve catalyst comprising a molecular sieve catalyst obtained according to the method of any of the above.
According to still another aspect of the present application, there is provided a process for preparing acetic acid, methyl acetate, by contact-reacting a compound I with a carbon monoxide-containing gas mixture in the presence of a catalyst to obtain methyl acetate or acetic acid; wherein the catalyst is at least one of the molecular sieve catalyst described in any one of the above and the molecular sieve catalyst prepared according to any one of the above methods; the compound I is at least one selected from methanol, halogenated methane and dimethyl ether.
Alternatively, the conditions of the reaction are: the temperature is 150-320 ℃, the pressure is 0.5-25.0 MPa, and the time is 10-24 h.
Alternatively, the upper pressure limit of the reaction is selected from 1MPa, 1.5MPa, 2MPa, 3MPa, 3.5MPa, 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, 22MPa or 25MPa; the lower limit is selected from 0.5MPa, 1MPa, 1.5MPa, 2MPa, 3MPa, 3.5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa or 22MPa.
Alternatively, the upper temperature limit of the reaction is selected from 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃, 260 ℃, 280 ℃, 300 ℃, or 320 ℃; the lower limit is selected from 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃, 260 ℃, 280 ℃ or 300 ℃.
Alternatively, the upper time limit of the reaction is selected from 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h; the lower limit is selected from 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h.
Alternatively, the conditions of the reaction are: the temperature is 160-320 ℃, the pressure is 1.0-20.0 MPa, and the time is 10-24 h.
Preferably, the conditions of the reaction are: the temperature is 170-300 ℃, the pressure is 1.0-15.0 MPa, and the time is 10-24 h.
Optionally, the feeding mass space velocity of the compound I is 0.05-5 h -1.
Optionally, the upper limit of the feed mass space velocity of compound I is selected from 0.08h-1、0.1h-1、0.25h-1、0.5h-1、0.8h-1、1.0h-1、1.50h-1、1.75h-1、2.00h-1、2.50h-1、3.00h-1、3.50h-1、4.00h-1、4.50h-1 or 5.00h -1; the lower limit is selected from 0.05h-1、0.08h-1、0.1h-1、0.25h-1、0.5h-1、0.8h-1、1.0h-1、1.50h-1、1.75h-1、2.00h-1、2.50h-1、3.00h-1、3.50h-1、4.00h-1 or 4.50h -1.
Optionally, the feeding mass space velocity of the compound I is 0.1-4.5 h -1.
Preferably, the feed mass space velocity of the compound I is 0.1-4 h -1.
Optionally, the molar ratio of carbon monoxide to compound I is from 0.1:1 to 50:1.
Optionally, the upper molar ratio of carbon monoxide to compound I is selected from 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 6:1, 8:1, 10:1, 15:1, 18:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 or 50:1; the lower limit is selected from 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 6:1, 8:1, 10:1, 15:1, 18:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 45:1.
Optionally, the molar ratio of carbon monoxide to compound I is from 0.5:1 to 50:1.
Optionally, the molar ratio of carbon monoxide to compound I is from 0.1:1 to 40:1.
Optionally, the molar ratio of carbon monoxide to compound I is from 0.5:1 to 40:1.
Preferably, the molar ratio of carbon monoxide to compound I is from 0.5:1 to 25:1.
Optionally, the volume fraction of carbon monoxide in the carbon monoxide-containing mixed gas is 20-100%.
Optionally, the mixed gas containing carbon monoxide further comprises an inert gas. The inactive gas is at least one selected from hydrogen, nitrogen, argon, carbon dioxide, methane and ethane.
Optionally, the reactor is a fixed bed reactor.
Alternatively, the selectivity of methyl acetate is greater than 98% when the compound I is selected from dimethyl ether.
Alternatively, the selectivity of acetic acid is greater than 85% when the compound I is selected from methanol.
Alternatively, the selectivity of methyl acetate + acetic acid is greater than 80% when the compound I is selected from methyl halides.
The application has the beneficial effects that:
1) The invention provides a catalyst for preparing methyl acetate and/or acetic acid, which has the advantages that the strong acid amount of a mordenite molecular sieve and the proportion of strong acid sites in an 8-membered ring pore canal are obviously increased after organic alkali treatment, and the catalyst has higher activity and target product selectivity.
2) The invention provides a modification method of a molecular sieve, which is characterized in that through organic alkaline water heat treatment, hydroxyl ions can dissolve skeleton atoms, but not the skeleton atoms can be recrystallized into the skeleton atoms under the induction of organic alkaline cations, so that the acid distribution, acid quantity and acid density of mordenite can be regulated and controlled on the premise of not obviously influencing the morphology, size and pore structure of crystals, the regulation and control of the acid position of the molecular sieve catalyst can be realized, and a new strategy is provided for the preparation of the molecular sieve catalyst.
3) The catalyst of the invention can be applied to a plurality of reactions, including dimethyl ether carbonylation, methanol carbonylation and halogenated methane carbonylation, and has wide adjustable range of reaction process conditions and universality.
Detailed Description
The present application will be described in detail with reference to specific examples, but the present application is not limited to the examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The product analysis method in the embodiment of the application is as follows: the reacted gas is led into an online gas chromatograph for analysis through a pipeline. The gas chromatograph model was Agilent 7890A, equipped with PLOT Q capillary column and TDX-1 packed column, with outlets connected to FID detector and TCD detector, respectively.
The conversion of small molecules and the selectivity of the products in the examples of the application were calculated as follows:
in the examples, the conversion of dimethyl ether or methanol or methyl chloride and the selectivity of the product are calculated on the basis of the moles of small molecules:
Conversion of dimethyl ether = [ (moles of dimethyl ether in feed gas) - (moles of dimethyl ether in product) ] ≡ (moles of dimethyl ether in feed gas) × (100%)
Methanol conversion = [ (moles of methanol carbon in feed gas) - (moles of methanol carbon in product) ] ≡ (moles of methanol carbon in feed gas) × (100%)
Methyl chloride conversion = [ (moles of methyl chloride carbon in the feed gas) - (moles of methyl chloride carbon in the product) ] ≡ (moles of methyl chloride carbon in the feed gas) × (100%)
Methyl acetate selectivity of dimethyl ether carbonylation = (2/3) × (moles of methyl acetate carbon in product)/(moles of dimethyl ether carbon in feed gas) - (moles of dimethyl ether carbon in product) ]× (100%)
Acetic acid selectivity for methanol carbonylation = (1/2) × (moles of acetic acid in product)/(moles of methanol in feed gas) - (moles of methanol in product) ]× (100%)
Acetic acid selectivity of halomethane carbonylation = (1/2) × (moles of acetic acid in product)/(moles of chloromethane in feed gas) - (moles of chloromethane in product) ]× (100%)
Example 1
10 G of NH 4 -MOR (Si/Al=10) molecular sieve are respectively placed into 100ml of tetraethylammonium hydroxide solution with the mass fraction of 3.0% (the solid-to-liquid ratio is 1g:10 ml), stirred until the mixture is uniform, then transferred into a 150ml high-pressure sealed reaction kettle, treated for 48 hours at 180 ℃, filtered, washed by deionized water and dried to obtain a solid sample. The prepared sample is roasted for 4 hours at 550 ℃ in air atmosphere to prepare the catalyst No. 1.
Example 2
The catalysts 2# and 3# were prepared in this order, with the other conditions being the same as in example 1, except that NH 4 -MOR (Si/Al=10) in example 1 was replaced with Na-MOR (Si/Al=10) and H-MOR (Si/Al=10)
Example 3
The molar ratio of NH 4 to MOR in example 1 was changed to 6, 15, 20, 50, respectively, and then catalysts 4#, 5#, 6#, 7# were prepared in that order, in the same manner as in example 1.
Example 4
Other conditions of the tetraethylammonium hydroxide in example 1 were changed to tetramethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide in the same manner as in example 1, and catalysts # 8, # 9 and # 10 were prepared in this order.
Example 5
The treatment temperature in example 1 was changed to 50℃at 100℃at 150℃at 170℃at 200℃at 220℃and the other conditions were kept the same, whereby catalysts 11#, 12#, 13#, 14#, 15#, 16# were produced in this order.
Example 6
The treatment time in example 1 was changed to 5 hours, 12 hours, 18 hours, 36 hours, 72 hours, and 100 hours, and the other conditions were kept the same, so that catalysts 17#, 18#, 19#, 20#, 21#, and 22#, were sequentially produced.
Example 7
The solid-to-liquid ratio in example 1 was changed to 1g:2ml, 1g:8ml, 1g:15ml, and 1g:20ml, and the other conditions were kept the same, so as to prepare catalysts 23#, 24#, 25#, and 26#, in that order.
Example 8
The mass concentrations of tetraethylammonium hydroxide in example 1 were changed to 1.5%, 4.5%, 7.5%, 10.5% and 15.0%, and the other conditions were kept the same, so that catalysts 27#, 28#, 29#, 30#, 31#, were prepared in this order.
Example 9
The tetraethylammonium hydroxide in example 1 was replaced with ethylenediamine, triethylamine, n-butylamine organic amine, and the other conditions were kept the same to prepare catalysts 32#, 33#, 34# in that order.
Example 10
The tetraethylammonium hydroxide in example 1 was replaced with triethylamine, and the mass percentage of triethylamine in the aqueous solution was 0.5%, 10%, 25%, 50%, 75%, 100%, and the other conditions were the same as in example 1, whereby catalysts 35#, 36#, 37#, 38#, 39#, 40# were produced in this order.
Example 11
The solid samples prepared in example 1 were calcined in dry air for 1.5 hours, 3 hours, 5 hours, 6 hours, and 10 hours under the same conditions to obtain catalysts 41#, 42#, 43#, 44#, and 45# in this order.
Example 12
The calcination temperature in example 1 was changed to 450 ℃, 500 ℃, 600 ℃, 650 ℃ and the other conditions were kept the same, and catalysts 46#, 47#, 48#, 49# were prepared in this order.
Example 13
The above catalyst examined the performance of dimethyl ether carbonylation to produce methyl acetate according to the following conditions.
0.5G of catalyst is filled into a fixed bed reactor with the inner diameter of 8mm, the temperature is increased to 400 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, the temperature is reduced to 200 ℃ under the same atmosphere, the pressure of a reaction system is increased to 2MPa by using a reaction mixture gas, and the reaction mixture gas passes through a catalyst bed layer from top to bottom. Wherein the dimethyl ether feeding airspeed is 1.0h -1; the molar ratio of carbon monoxide to dimethyl ether is 6:1, the carbon monoxide raw material gas contains hydrogen, the catalytic reaction is operated for 10 hours, and the reaction result is shown in table 1.
TABLE 1 evaluation results of dimethyl ether carbonylation catalysis with different catalysts
Example 14
The above catalyst was examined for acetic acid production performance by methanol carbonylation under the following conditions.
The experimental catalysts were 1#, 5#, 10#, 15# samples, 1 gram of the catalyst was loaded into a fixed bed reactor with an inner diameter of 8mm, the temperature was raised to 400 ℃ at a rate of 2 ℃/min under a nitrogen atmosphere, the temperature was maintained for 2 hours, then the temperature was lowered to a reaction temperature of 280 ℃ under the same atmosphere, the pressure of the reaction system was raised to 2MPa by using a reaction mixture, and the reaction mixture was passed through the catalyst bed from top to bottom. Wherein the methanol feeding space velocity is 1.0h -1, the molar ratio of carbon monoxide to methanol is 50:1, the carbon monoxide raw material gas contains hydrogen, the catalytic reaction is operated for 10 hours, and the reaction structure is shown in table 2.
TABLE 2 evaluation results of methanol carbonylation catalysis with different catalysts
Example 15
The above catalyst was examined for acetic acid production performance by carbonylation of methyl halide under the following conditions.
The catalyst used in the experiment was sample No. 5, 1g of the catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, the temperature was raised to 400℃at a rate of 2℃per minute under a nitrogen atmosphere, the temperature was maintained for 2 hours, and then the temperature was lowered to 260℃under the same atmosphere, and the pressure of the reaction system was raised to 2.5MPa with a reaction mixture (chloromethane/CO or bromomethane/CO or iodomethane/CO) while the reaction mixture was passed through the catalyst bed from top to bottom. Wherein the space velocity of the halomethane feed is 0.5h -1, the molar ratio of carbon monoxide to the halomethane is 20:1, the carbon monoxide feed gas does not contain other gases, the catalytic reaction is operated for 20 hours, and the reaction structure is shown in table 3.
TABLE 3 evaluation of the carbonylation of halomethanes
Example 16
And (3) the reaction results of the methyl acetate production by dimethyl ether carbonylation at different reaction temperatures.
The catalyst tested was sample # 1, 0.5 gram of catalyst was charged into a fixed bed reactor having an inner diameter of 8mm, heated to 400 c at a rate of 2 c/min under nitrogen atmosphere, held for 2 hours, and then lowered to the reaction temperature under the same atmosphere. The pressure of the system is increased to 2MPa by using the reaction mixture, and the reaction gas passes through the catalyst bed layer from top to bottom. Wherein the dimethyl ether feeding airspeed is 1.0h -1; the molar ratio of carbon monoxide to dimethyl ether is 6:1, and the carbon monoxide raw material gas contains hydrogen, and the reaction temperature is 170 ℃, 190 ℃,210 ℃, 230 ℃ and 300 ℃ respectively. The catalytic reaction was run for 10 hours and the results are shown in Table 4.
TABLE 4 reaction results at different reaction temperatures
| Reactor inlet temperature (. Degree. C.) | 170 | 190 | 210 | 230 | 300 |
| Dimethyl ether conversion (%) | 26.7 | 31.2 | 40.1 | 46.5 | 53.2 |
| Methyl acetate selectivity (%) | 98.6 | 99.2 | 98.9 | 98.5 | 98.2 |
| Other substance Selectivity (%) | 1.4 | 0.8 | 1.1 | 1.5 | 1.8 |
Example 17
And (3) carrying out the reaction results of dimethyl ether carbonylation to produce methyl acetate under different reaction pressures.
The experimental catalyst was sample # 1, the reaction pressures were 1, 3, 5 and 15Mpa, respectively, the reaction temperature was 200 ℃, and the other procedures were the same as in example 16. The reaction was run for 10 hours and the results are shown in Table 5.
TABLE 5 reaction results at different reaction pressures
| Reaction pressure (MPa) | 1 | 3 | 5 | 15 |
| Dimethyl ether conversion (%) | 16.8 | 42.5 | 62.4 | 72.1 |
| Methyl acetate selectivity (%) | 98.6 | 99.0 | 99.4 | 99.6 |
| Other substance Selectivity (%) | 1.4 | 1.0 | 0.6 | 0.4 |
Example 18
Dimethyl ether carbonylation reaction results at different dimethyl ether space velocities.
The catalyst used in the experiment was sample # 1, the feed mass space velocity of dimethyl ether was 0.1h -1、1.5h-1、1.75h-1、2.0h-1、2.5h-1 and 4h -1, the reaction temperature was 200 ℃, the other operating conditions were the same as in example 16, and the reaction results are shown in Table 6.
TABLE 6 reaction results at different dimethyl ether space velocities
| Dimethyl ether feeding airspeed (h -1) | 0.1 | 1.5 | 1.75 | 2.0 | 4.0 |
| Dimethyl ether conversion (%) | 100 | 55.8 | 36.7 | 24.8 | 5.7 |
| Methyl acetate selectivity (%) | 99.7 | 99.6 | 99.5 | 99.6 | 99.3 |
| Other substance Selectivity (%) | 0.3 | 0.4 | 0.5 | 0.4 | 0.7 |
Example 19
Reaction results at different molar ratios of carbon monoxide to dimethyl ether.
The experimental catalyst was sample # 1, the molar ratio of carbon monoxide to dimethyl ether was 0.1:1, 0.5:1, 1:1, 2:1, 5:1, 10:1, 15:1 and 25:1, the reaction temperature was 200 ℃, the other operating conditions were the same as in example 16, and the reaction results are shown in table 7.
TABLE 7 reaction results at different carbon monoxide to dimethyl ether molar ratios
Example 20
And (c) a result of the dimethyl ether carbonylation reaction when the feed gas containing carbon monoxide contains an inert gas.
The experimental catalyst is a sample No. 1, the feeding space velocity of dimethyl ether is 0.5h -1, the feed gas containing carbon monoxide contains inactive gas, the mol ratio of the feed gas containing carbon monoxide to dimethyl ether is 5:1, other conditions are the same as in example 13, and the reaction results are shown in Table 8.
TABLE 8 reaction results of inactive gas contained in carbon monoxide-containing raw gas
Example 21
And (3) the reaction results of the carbonylation of methyl chloride to produce acetic acid/methyl acetate at different reaction temperatures.
The catalyst tested was sample # 5, 1.0 gram of catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, heated to 400 c at a rate of 2 c/min under nitrogen atmosphere, held for 2 hours, and then lowered to the reaction temperature under the same atmosphere. The pressure of the system is raised to 2.5MPa by using the reaction mixture, and the reaction gas passes through the catalyst bed layer from top to bottom. Wherein the space velocity of methyl chloride feed is 0.5h -1; the molar ratio of carbon monoxide to chloromethane is 20:1, and the reaction temperature is 180 ℃, 230 ℃, 280 ℃ and 300 ℃ respectively. The catalytic reaction was run for 20 hours and the results are shown in Table 9.
TABLE 9 carbonylation results at various reaction temperatures for chloromethane
| Reactor inlet temperature (. Degree. C.) | 180 | 230 | 280 | 300 |
| Methyl chloride conversion (%) | 15.6 | 26.7 | 45.6 | 71.9 |
| Acetic acid+methyl acetate selectivity (%) | 99.7 | 96.7 | 88.5 | 80.5 |
| Other substance Selectivity (%) | 0.3 | 3.3 | 11.5 | 19.5 |
Example 22
The reaction results of methyl chloride carbonylation to acetic acid/methyl acetate were carried out at different reaction pressures.
The catalyst used in the experiment was sample # 14, the reaction pressures were 1.5, 3.5, 5 and 15Mpa, respectively, the reaction temperature was 260 c, and the other procedures were the same as in example 21. The reaction was run for 20 hours and the results are shown in Table 10.
TABLE 10 results of chloromethane carbonylation at various reaction pressures
Example 23
Reaction results at different molar ratios of carbon monoxide to methyl chloride.
The molar ratios of carbon monoxide to methyl chloride were 0.1:1, 5:1, 10:1 and 25:1, the reaction temperature was 260℃and the other operating conditions were the same as in example 21, and the reaction results are shown in Table 11.
TABLE 11 reaction results of different carbon monoxide to methyl chloride molar ratios
| Carbon monoxide to chloromethane molar ratio | 0.1:1 | 5:1 | 10:1 | 25:1 |
| Methyl chloride conversion (%) | 6.7 | 13.2 | 21.8 | 40.9 |
| Acetic acid+methyl acetate selectivity (%) | 86.1 | 90.1 | 98.2 | 98.8 |
| Other substance Selectivity (%) | 13.9 | 9.9 | 1.8 | 1.2 |
Example 24
10 G of NH 4 -MOR (Si/Al=10) molecular sieve are respectively placed into 100ml of tetraethylammonium hydroxide solution with mass fraction of 3.0% (solid-to-liquid ratio is 1g:10 ml), stirred and mixed uniformly, treated for 48 hours at 50 ℃, 100 ℃ and 150 ℃ under normal pressure, filtered, washed by deionized water and dried to obtain a solid sample. The prepared samples were calcined under an air atmosphere at 550 c for 4 hours to prepare catalysts 50#, 51# and 52#. And examined the performance of dimethyl ether carbonylation to methyl acetate under the same conditions as in example 13, see in particular table 12.
TABLE 12 comparison of dimethyl ether carbonylation performance of catalysts treated under non-closed versus closed conditions
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended to cover the principles of the application as defined in the appended claims.
Claims (4)
1. A process for the preparation of acetic acid and methyl acetate, characterized in that methyl halide and carbon monoxide are contacted in the presence of a catalyst to obtain methyl acetate and acetic acid;
Wherein the reaction temperature is 150-320 ℃, the reaction pressure is 0.5-25.0 MPa, and the reaction time is 10-24 h; the feeding mass airspeed of the halogenated methane is 0.05-5 h -1;
The molar ratio of the carbon monoxide to the halogenated methane is 0.1:1-50:1;
Wherein the catalyst is a molecular sieve catalyst;
the preparation method of the molecular sieve catalyst comprises the following steps:
S1, mixing a mordenite molecular sieve and an organic alkali source, and treating for 5-100 hours at 50-220 ℃ in a closed reaction kettle; obtaining an intermediate product;
The mordenite molecular sieve is selected from at least one of Na-MOR, NH 4 -MOR and H-MOR molecular sieves;
the organic alkali source is alkyl ammonium hydroxide; the alkyl ammonium hydroxide is selected from at least one of compounds having a chemical formula shown in formula II:
a formula II;
Wherein R 4,R5,R6,R7 is independently selected from any one of the alkyl groups of C 1~C10;
the ratio of the adding amount of the mordenite molecular sieve to the adding amount of the organic alkali source is 1g:2 mL-1 g:20mL;
and S2, roasting the intermediate product to obtain the molecular sieve catalyst.
2. The method of claim 1, wherein the firing conditions are: the temperature is 450-650 ℃ and the time is 1.5-10 hours.
3. The process of claim 1 wherein the mordenite molecular sieve has a silicon to aluminum atomic ratio of: si/al=6 to 50.
4. The method of claim 1, wherein the organic alkali source further comprises a solvent; the solvent is selected from water;
the mass content of the organic alkali in the organic alkali source is 0.5-99.9%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190315A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Mordenite with compound hole structure and preparation method thereof |
| CN103964459A (en) * | 2013-01-31 | 2014-08-06 | 中国石油化工股份有限公司 | Modification method of molecular sieve |
| CN111790452A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院大连化学物理研究所 | Methanol carbonylation catalyst, preparation method and application thereof |
| CN111792994A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院大连化学物理研究所 | Method for producing methyl acetate by dimethyl ether carbonylation |
| CN112390704A (en) * | 2019-08-13 | 2021-02-23 | 中国科学院大连化学物理研究所 | Method for preparing methanol and acetic acid by directly converting methane |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190315A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Mordenite with compound hole structure and preparation method thereof |
| CN103964459A (en) * | 2013-01-31 | 2014-08-06 | 中国石油化工股份有限公司 | Modification method of molecular sieve |
| CN111790452A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院大连化学物理研究所 | Methanol carbonylation catalyst, preparation method and application thereof |
| CN111792994A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院大连化学物理研究所 | Method for producing methyl acetate by dimethyl ether carbonylation |
| CN112390704A (en) * | 2019-08-13 | 2021-02-23 | 中国科学院大连化学物理研究所 | Method for preparing methanol and acetic acid by directly converting methane |
Non-Patent Citations (2)
| Title |
|---|
| "Identifying and controlling the acid site distributions in mordenite zeolite for dimethyl ether carbonylation reaction by means of selective ion-exchange";Shiping Liu等;《Catal. Sci. Technol》;第10卷;4663-4672 * |
| "超声波碱处理改性对丝光沸石结构、酸性质及其催化性能的影响";韩海波等;韩海波等;第69卷(第7期);3001-3008 * |
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