CN116639704A - 一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法及其应用 - Google Patents
一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法及其应用 Download PDFInfo
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- CN116639704A CN116639704A CN202310463834.5A CN202310463834A CN116639704A CN 116639704 A CN116639704 A CN 116639704A CN 202310463834 A CN202310463834 A CN 202310463834A CN 116639704 A CN116639704 A CN 116639704A
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- Prior art keywords
- silicon
- molecular sieve
- acid
- hydroxide
- mordenite molecular
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 54
- 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 54
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 34
- 239000010703 silicon Substances 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title claims description 4
- 239000002243 precursor Substances 0.000 claims abstract description 23
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000012670 alkaline solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001308 synthesis method Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010306 acid treatment Methods 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 239000012141 concentrate Substances 0.000 claims abstract description 6
- 239000010413 mother solution Substances 0.000 claims abstract description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 43
- 239000012452 mother liquor Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005810 carbonylation reaction Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 230000006315 carbonylation Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- -1 cyclopentane amine Chemical class 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 4
- QXNDZONIWRINJR-UHFFFAOYSA-N azocane Chemical compound C1CCCNCCC1 QXNDZONIWRINJR-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- JVQOASIPRRGMOS-UHFFFAOYSA-M dodecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)C JVQOASIPRRGMOS-UHFFFAOYSA-M 0.000 claims description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 4
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 4
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 4
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 9
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QECJIGNJADOMIG-UHFFFAOYSA-N [C].COC Chemical compound [C].COC QECJIGNJADOMIG-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
- C01B39/265—Mordenite type using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/86—Borosilicates; Aluminoborosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/04—Formic acid esters
- C07C69/06—Formic acid esters of monohydroxylic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
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Abstract
本申请公开了一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法及其应用,属于分子筛领域。一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法,包括以下步骤:S1、获得母液浓缩液和硼源制成的硅硼前驱体;S2、获得含铝的碱性溶液;S3、将含有所述硅硼前驱体、所述碱性溶液的混合物水热晶化后,得到产物;S4、将上述产物在水蒸气下进行热处理和/或酸处理,得到所述高硅丝光沸石分子筛。该方法在提高酸强度和8元环酸比例的同时,使得反应低温活性更佳;分子筛合成固体废物极大减少;分子筛放大生产污水处理成本降低;相同条件下较目前初始反应温度显著降低;催化剂单程寿命可大幅提高。
Description
技术领域
本申请涉及一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法及其应用,属于分子筛领域。
背景技术
丝光沸石是一种结晶的微孔硅铝酸盐,具有十二元环和八元环的孔道结构及适宜的酸性以及良好的水热稳定性,已成为重要的石油化工和煤化工领域的催化材料,特别是最近应用在二甲醚羰基化制乙酸甲酯的反应中。
乙酸甲酯是一种重要的化工产品和良好的环保有机溶剂,广泛应用于树脂和皮革等生产中。其下游产品乙酸,乙酸酯、醋酐和乙醇等均是重要的化工原料。乙酸甲酯加氢可以得到乙醇,后者是一种重要的有机溶剂和燃料添加剂,作为汽油添加剂可以提高辛烷值、促进燃烧、降低污染物排放,乙醇的大规模工业生产可以有效缓解我国长期以来原油对外依存度较高的窘境。
以二甲醚羰基化制备乙酸甲酯,再进一步加氢制备乙醇的技术路径,打通了一个由非石油基含碳资源到制备清洁能源乙醇的高效路径。因此研究二甲醚羰基化制备乙酸甲酯的催化反应具有重要意义。
2006年,Iglesia小组首次报道了无卤素、不含贵金属条件下酸性分子筛催化DME羰基化反应(Angewandte Chemie,Int.Ed.2006,45(10),1617-1620)。他们利用红外光谱对分子筛的酸分布进行表征,利用不同动力学直径的探针分子确定八元环孔道内数量,并将酸量与羰基活性进行关联,发现羰基化反应活性与八元环内的/>酸中心数量成正比(Acc.Chem.Res.2008,41,4,559-567)。
羰基化催化反应是强放热反应,催化剂在长期使用过程中需要具备较高的活性和稳定性。因此控制铝落位在八元环内并形成较强的酸性位将是提高丝光沸石作为二甲醚羰基化催化剂的反应活性和稳定性的有效手段。CN 201611135717.2公开了一种B酸中心落位和分布可调变丝光沸石(MOR)分子筛的合成方法,制备得到的MOR沸石B酸中心优先落位在与12元环孔道相连通的8元环的“侧口袋”中,通过该方法获得的催化剂产品在吸附和催化方面表现出优异的性能。
CN202011582829.9公开了一种高硅铝比丝光沸石的制备方法及其应用通过预晶化,得到高硅铝比前驱体及结构导向溶胶的作用,得到硅铝比在15~50的丝光沸石,其二甲醚羰基化制备乙酸甲酯性能优异。
专利CN108160100A采用吡啶与和硝酸盐分别对HMOR十二元环和八元环进行改性,改进了催化剂的稳定性。CN202111644362.0公开了一种铝落位控制的丝光沸石分子筛合成方法,其结构内八元环铝落位占比高于50%。专利CN201510117253.1公开了一种兼具微孔和介孔结构的丝光沸石的合成方法。
Liu等通过选择性离子交换得到了八元环酸性位占32%的丝光沸石,催化剂DME转化率达50%,使用寿命达210h以上(Catal.Sci.Technol.,2020,10,4663-4672)。Liu等(Catalysis Communications,2020,147,106161)在MOR沸石中引入1,3-二甲基咪唑鎓离子可以选择性地去除十二元环(12MR)通道中的酸位,从而显着提高稳定性和活性,但催化剂的生产成本显著增加。
发明内容
本发明提供了一种反应活性位可及性更佳的高硅的丝光沸石分子筛合成方法,该丝光沸石分子筛通过利用母液浓缩液并向合成体系引入硼,并通过后期的水热和/或酸处理,使沸石分子筛孔道更为通畅,反应的活性位可及性更佳。将其作为二甲醚羰基化合成乙酸甲酯的催化剂,二甲醚的转化反应温度明显降低,转化率提高,说明其活性位可及性更佳,其低温活性要明显优于同样条件一步法合成的丝光沸石分子筛。
根据本申请的第一个方面,提供了一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法。
一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法,包括以下步骤:
S1、获得母液浓缩液和硼源制成的硅硼前驱体;
S2、获得含铝的碱性溶液;
S3、将含有所述硅硼前驱体、所述碱性溶液的混合物水热晶化后,得到产物;
S4、将上述产物在水蒸气下进行热处理和/或酸处理,得到所述高硅丝光沸石分子筛。
热处理的气氛包括空气、氮气。
可选地,所述硅硼前驱体的制备如下:
将含有硅源、硼源、模板剂A、水、母液浓缩液的物料,搅拌陈化后制成所述硅硼前驱体。
可选地,所述碱性溶液的制备如下:
将含有铝源、碱源,模板剂B、水的物料,搅拌陈化后制成所述碱性溶液。
可选地,步骤S3中,对包含产物的母液进行分离、蒸馏得到所述母液浓缩液。
母液浓缩液制备方法如下:
1)将第一次合成的分子筛固体产物进行过滤分离,然后将母液进行回收;
2)分析回收母液中各组分含量;
3)将母液装填至密闭容器内,加热蒸馏出一定量水分,获得浓缩液;
4)分析母液浓缩液中各组分含量。
可选地,步骤S3中,水热晶化的条件如下:
温度为120~200;
时间为12~120h。
可选地,所述水热晶化的条件包括:晶化的温度为60~150,晶化的时间为2~15h。
可选地,步骤S4中,热处理的条件如下:
温度为80~200;
时间为0.5~2.0h。
可选地,所述酸处理包括将产物置于一定浓度酸溶液中。
可选地,产物的质量与酸的体积比为3~10:1。
可选地,所述酸选自硫酸、硝酸、盐酸、柠檬酸、醋酸等中的至少一种。
可选地,酸处理的条件如下:
温度为55~85;
时间为0.5~2.5h。
可选地,所述硅源选自溶胶、水玻璃、白炭黑、硅藻土中的至少一种。
可选地,所述硼源选自硼酸。
可选地,所述模板剂A选自十六烷基三甲基溴化铵、十二烷基三甲基溴化铵、四丙基溴化铵、四乙基溴化铵、四甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基氯化铵、四丙基氯化铵、四乙基氯化铵,四甲基氯化铵、十六烷基三甲基氢氧化铵、十二烷基三甲基氢氧化铵、四丙基氢氧化铵、四乙基氢氧化铵、四甲基氢氧化铵、三乙胺、异丙胺、二异丙胺、三异丙胺、正丁胺、环己胺、己内酰胺、六亚甲基亚胺、七亚甲基亚胺、环庚烷胺、环戊烷胺中的至少一种。
可选地,所述物料中的原料摩尔配比为:
M2O:SiO2:B2O3:模板剂A:H2O=(0.06~0.50):1:(0.01~0.15):
(0.01~0.12):(10~150)。
可选地,所述铝源选自铝酸钠、异丙醇铝、氢氧化铝、硫酸铝中的至少一种。
可选地,所述碱源选自碱金属氢氧化物、氧化物中的至少一种。
可选地,所述碱源选自氢氧化钾、氢氧化钠中的至少一种。
可选地,模板剂B选自十六烷基三甲基溴化铵、十二烷基三甲基溴化铵、四丙基溴化铵、四乙基溴化铵、四甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基氯化铵、四丙基氯化铵、四乙基氯化铵,四甲基氯化铵、十六烷基三甲基氢氧化铵、十二烷基三甲基氢氧化铵、四丙基氢氧化铵、四乙基氢氧化铵、四甲基氢氧化铵、三乙胺、异丙胺、二异丙胺、三异丙胺、正丁胺、环己胺、己内酰胺、六亚甲基亚胺、七亚甲基亚胺、环庚烷胺、环戊烷胺中的至少一种。
可选地,加入物料后凝胶摩尔配比为:
SiO2:Al2O3:B2O3:M2O:H2O:T=1:(0.01~0.1):(0.02~0.45):
(0.05~0.3):(10~50):(0.01~0.30)。
可选地,陈化的条件如下:
温度为40~120;
时间为4~12h。
根据本申请的一个实施方式,一种反应活性位可及性更佳的高硅的丝光沸石分子筛合成方法,所述方法至少包含以下步骤:
(1)硅硼前驱体制备:将硅源、硼源、模板剂A、水和母液浓缩液按一定比例一定温度条件下搅拌陈化后制成硅硼前驱体;碱性溶液的制备:将铝源、碱源,模板剂B和水按一定比例一定温度条件下搅拌陈化后制成碱性溶液;
(2)所述碱性溶液按一定比例加入硅硼前驱体中,在不锈钢高压釜中进行水热晶化反应,产物经洗涤干燥后经酸水热和处理,得到反应可及性更佳的高硅丝光沸石分子筛;产物分离后的母液经蒸馏得到母液浓缩液经组分分析后可用于上述硅硼前驱体的制备。
所述方法合成的丝光沸石步骤(1)中硅硼前驱体和碱性溶液制备条件为:温度为40~120,时间为4~12h;
步骤(2)中,所述水热和酸处理是指在含有水蒸气的条件下,对分子筛粉末进行热处理,然后再进行酸处理。
根据本申请的第二个方面,提供了一种高硅丝光沸石分子筛。
上述所述的合成方法得到的高硅丝光沸石分子筛,所述高硅丝光沸石分子筛的硅铝比为15~85。
可选地,所述高硅丝光沸石分子筛的总酸量为550~700μmol/g。
可选地,所述高硅丝光沸石分子筛的比表面积为350~450m2/g。
根据本申请的第三个方面,提供了一种高硅丝光沸石分子筛的应用。
上述所述的合成方法得到的高硅丝光沸石分子筛和/或上述所述的高硅丝光沸石分子筛作为催化剂在二甲醚羰基化的应用。
本申请能产生的有益效果包括:
1)本申请所提供的一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法,在提高酸强度和8元环酸比例的同时,使得反应低温活性更佳;分子筛合成固体废物极大减少;分子筛放大生产污水处理成本降低;相同条件下较目前初始反应温度显著降低;催化剂单程寿命可大幅提高。
2)本申请所提供的一种高硅丝光沸石分子筛的应用,将其作为二甲醚羰基化合成乙酸甲酯的催化剂,二甲醚的转化反应温度明显降低,转化率提高,说明其活性位可及性更佳,其低温活性要明显优于同样条件一步法合成的丝光沸石分子筛。
附图说明
图1为本申请实施例2、4、6和对比例1的XRD。
具体实施方式
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
如无特别说明,本申请的实施例中的原料均通过商业途径购买。
二甲醚吸附实验在梅特勒-托莱多热重分析仪(TGA/DSC 3+)上进行。样品(约30毫克)在测试前先在350的高真空条件下脱水6小时。然后,将样品转移到热重分析仪中,并在50下稳定,然后将二甲醚(5.0v%DME在Ar中平衡)引入系统进行吸附。
傅里叶红外光谱
红外拟合,红外光谱采用Bruke Tensor II光谱仪,配备真空原位池。首先,5mg粉末状样品被压制成的自支撑圆片,之后放入原位红外池中,接着在400(升温速率为5/min)、真空条件下预处理1h,除去样品中的水。预处理后,降至室温,进行红外光谱扫描,扫描范围为4000-600cm-1,扫描次数为32,分辨率为4cm-1。
氮气物理吸附脱附
氮气物理吸附实验在康塔公司Autosorb-iQ仪器上进行,首先称取0.05g分子筛样品(20目-40目)于物理吸附管中。测试前,样品先在350、真空条件下预处理6h,除去吸附的水和其他表面物质。之后,在液氮温度77K下进行氮气物理吸附和脱附测试。采用BET方程计算得到样品的比表面积,以相对压力最高点时的氮气吸附量计算得到分子筛的总孔容;利用t-plot方法计算得到样品的微孔比表面积、微孔体积;利用BJH法计算得到样品的孔径分布;利用DFT方法计算孔宽和总孔分布。
X射线衍射仪(XRD)
日本理学公司的SmartLab SE型X射线衍射仪,样品测试条件:Cu靶,Kα射线(λ=0.1542nm),管电压40kV,管电流30mA,扫描速率为20°/min,范围为3°~55°。
X射线荧光光谱(XRF)
利用日本理学公司的ZSX PrimusⅢ+型荧光光谱仪来分析样品的元素组成和含量。测试前,分子筛样品充分研磨成细小粉末,30MPa下压片后再放入测试池进行分析。
氨气程序升温脱附(NH3-TPD)
化学吸附分析采用美国AMI公司的AMI300化学吸附仪,将0.1g分子筛样品装入U型石英管中,首先在600、He气氛中预处理1h后降温至150,并通入NH3/He混合气,吸附0.5h。然后在He气气氛下吹扫0.5h除去物理吸附的NH3,待基线稳定后,以10°/min的速率升温至700,脱附的NH3用热导池检测器(TCD)进行记录。
反应性能评价:
在高压固定床反应装置上进行催化剂评价。反应管为316L不锈钢,内径为9mm,催化剂装填量为1.0g,尺寸为20-40目。原料气(DME:CO:H2=5:35:60),反应压力为2.0MPa,时空速率为1800mL/gcat/h。反应温度180,反应后的气体产物在线分析在磐诺A60或1949型气相色谱仪上进行,HP-PLOT/Q毛细柱,FID检测器。
本申请的实施例中转化率、选择性计算如下:
二甲醚转化率=[(原料气中二甲醚碳摩尔数)-(产物中二甲醚碳摩尔数)]÷(原料气中二甲醚碳摩尔数)×(100%);
乙酸甲酯选择性=(2/3)×(产物中乙酸甲酯碳摩尔数)÷[(原料气中二甲醚碳摩尔数)-(产物中二甲醚碳摩尔数)]×(100%)。
实施例1
硅硼前驱体的制备:
以NaOH为碱源、硼酸为硼源、硅酸钠为硅源、异丙醇铝为铝源、十六烷基三甲基氯化铵为模板剂A,取一定量母液浓缩液后混合后转移至反应釜中,100保持8h陈化后制成硅硼前驱体,其摩尔组成为SiO2:B2O3:Na2O:H2O:A=1:0.028:0.08:40:0.02;
碱性溶液的制备:
异丙醇铝、四乙基氢氧化铵和水按摩尔组成为Al2O3:Na2O:H2O:B=1:9.64:535:3.2,搅拌均匀,60陈化2h后降至室温,制成碱性溶液;
反应活性位可及性更佳的高硅丝光沸石分子筛的合成:
将一定量的硅硼前驱体和碱性溶液混合,加入后搅拌一段时间,升温至170保持72h,得到产物,产物分离后的母液经蒸馏得到母液浓缩液经组分分析后可用于上述硅硼前驱体的制备,再进行酸处理,得到所述高硅丝光沸石分子筛。
对比例1
实验步骤同实施例1,仅是在制备硅硼前驱体时,不加入硼源。
实施例2-6
实施例2-6的制备过程同实施例1,所制备的样品的硅硼前驱体、碱性溶液中的原料类型及配比、预晶化温度和时间、晶化温度和时间分别如表1所示。后续处理物料及方式具体参见表2。
表1
表2
分析例1
对实施例1-6,对比例1得到的分子筛催化剂进行硅铝比、TPD总酸量及物理吸附的测定,结果如表3。
表3
对实施例1-6,对比例1得到的分子筛催化剂进行二甲醚重量法吸附实验,结果如表4。
表4
由上述表征结果可以看出,在本申请合成和处理方法后,催化剂TPD总酸量增加,催化剂对二甲醚吸附时间平衡时间变短,使得催化剂的反应可及性更佳,对于羰基化反应,在相同反应温度下,二甲醚转化率增加。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
1.一种反应活性位可及性更佳的高硅丝光沸石分子筛的合成方法,其特征在于,包括以下步骤:
S1、获得母液浓缩液和硼源制成的硅硼前驱体;
S2、获得含铝的碱性溶液;
S3、将含有所述硅硼前驱体、所述碱性溶液的混合物水热晶化后,得到产物;
S4、将上述产物在水蒸气下进行热处理和/或酸处理,得到所述高硅丝光沸石分子筛。
2.根据权利要求1所述的合成方法,其特征在于,所述硅硼前驱体的制备如下:
将含有硅源、硼源、模板剂A、水、母液浓缩液的物料,搅拌陈化后制成所述硅硼前驱体。
3.根据权利要求1所述的合成方法,其特征在于,所述碱性溶液的制备如下:
将含有铝源、碱源,模板剂B、水的物料,搅拌陈化后制成所述碱性溶液。
4.根据权利要求1所述的合成方法,其特征在于,步骤S3中,对包含产物的母液进行分离、蒸馏得到所述母液浓缩液;
优选地,步骤S3中,水热晶化的条件如下:
温度为120~200;
时间为12~120h。
5.根据权利要求1所述的合成方法,其特征在于,步骤S4中,热处理的条件如下:
温度为80~200;
时间为0.5~2.0h;
优选地,所述酸处理包括将产物置于酸中:
优选地,产物的质量与酸的体积比为3~10:1;
优选地,所述酸选自硫酸、硝酸、盐酸、柠檬酸、醋酸等中的至少一种;
优选地,酸处理的条件如下:
温度为55~85;
时间为0.5~2.5h。
6.根据权利要求2所述的合成方法,其特征在于,所述硅源选自硅溶胶、水玻璃、白炭黑、硅藻土中的至少一种;
优选地,所述硼源选自硼酸;
优选地,所述模板剂A选自十六烷基三甲基溴化铵、十二烷基三甲基溴化铵、四丙基溴化铵、四乙基溴化铵、四甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基氯化铵、四丙基氯化铵、四乙基氯化铵,四甲基氯化铵、十六烷基三甲基氢氧化铵、十二烷基三甲基氢氧化铵、四丙基氢氧化铵、四乙基氢氧化铵、四甲基氢氧化铵、三乙胺、异丙胺、二异丙胺、三异丙胺、正丁胺、环己胺、己内酰胺、六亚甲基亚胺、七亚甲基亚胺、环庚烷胺、环戊烷胺中的至少一种;
优选地,所述物料中的原料摩尔配比为:
M2O:SiO2:B2O3:模板剂A:H2O=(0.06~0.50):1:(0.01~0.15):
(0.01~0.12):(10~150)。
7.根据权利要求3所述的合成方法,其特征在于,所述铝源选自铝酸钠、异丙醇铝、氢氧化铝、硫酸铝等中的至少一种;
优选地,所述碱源选自碱金属氢氧化物、氧化物中的至少一种;
优选地,所述模板剂B选自十六烷基三甲基溴化铵、十二烷基三甲基溴化铵、四丙基溴化铵、四乙基溴化铵、四甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基氯化铵、四丙基氯化铵、四乙基氯化铵,四甲基氯化铵、十六烷基三甲基氢氧化铵、十二烷基三甲基氢氧化铵、四丙基氢氧化铵、四乙基氢氧化铵、四甲基氢氧化铵、三乙胺、异丙胺、二异丙胺、三异丙胺、正丁胺、环己胺、己内酰胺、六亚甲基亚胺、七亚甲基亚胺、环庚烷胺、环戊烷胺中的至少一种中的至少一种;
优选地,加入物料后凝胶摩尔配比为:
SiO2:Al2O3:B2O3:M2O:H2O:T=1:(0.01~0.1):(0.02~0.45):
(0.05~0.3):(10~50):(0.01~0.30)。
8.根据权利要求2或3所述的合成方法,其特征在于,陈化的条件如下:
温度为40~120;
时间为4~12h。
9.权利要求1~8中任一项所述的合成方法得到的高硅丝光沸石分子筛,其特征在于,所述高硅丝光沸石分子筛的硅铝比为15~85;
优选地,所述高硅丝光沸石分子筛的总酸量为550~700μmol/g;
优选地,所述高硅丝光沸石分子筛的比表面积为400~450m2/g。
10.权利要求1~8中任一项所述的合成方法得到的高硅丝光沸石分子筛和/或权利要求9所述的高硅丝光沸石分子筛作为催化剂在二甲醚羰基化的应用。
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