CN111924854B - 一种ecnu-29钛铝硅酸盐纳米片及其制备方法和应用 - Google Patents
一种ecnu-29钛铝硅酸盐纳米片及其制备方法和应用 Download PDFInfo
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- CN111924854B CN111924854B CN202010848031.8A CN202010848031A CN111924854B CN 111924854 B CN111924854 B CN 111924854B CN 202010848031 A CN202010848031 A CN 202010848031A CN 111924854 B CN111924854 B CN 111924854B
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- aluminosilicate
- ketone
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- 239000010936 titanium Substances 0.000 title claims abstract description 58
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 55
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims abstract description 49
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002135 nanosheet Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- -1 aldehyde organic compounds Chemical class 0.000 claims abstract description 27
- 150000002576 ketones Chemical class 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000003586 protic polar solvent Substances 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012229 microporous material Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000000547 structure data Methods 0.000 claims description 5
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-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
- 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 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000002210 silicon-based material Substances 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
- 238000001228 spectrum Methods 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 238000006146 oximation reaction Methods 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 31
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 16
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 16
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 16
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 8
- DMJZWFZICOEEAJ-UHFFFAOYSA-N 2-(4-bromothiophen-3-yl)sulfanylpropanoic acid Chemical compound OC(=O)C(C)SC1=CSC=C1Br DMJZWFZICOEEAJ-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 150000002923 oximes Chemical class 0.000 description 6
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical group CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 3
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 2
- VTWKXBJHBHYJBI-VURMDHGXSA-N (nz)-n-benzylidenehydroxylamine Chemical compound O\N=C/C1=CC=CC=C1 VTWKXBJHBHYJBI-VURMDHGXSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FZENGILVLUJGJX-IHWYPQMZSA-N (Z)-acetaldehyde oxime Chemical compound C\C=N/O FZENGILVLUJGJX-IHWYPQMZSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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Abstract
本发明公开了一种ECNU‑29钛铝硅酸盐纳米片及其制备方法和应用,其特点是以ECNU‑29为骨架氧化物以四面体形式相互连接构成一种新型的二维有序微孔复合氧化物材料,其化学组成为:TipMm n+AlxSiOy;制备以含苄基的两亲性双季胺盐作为有机模板剂,通过水热合成和铵交换后焙烧,制得具有完整晶态结构的ECNU‑29,该催化剂在含有质子性溶剂的体系中催化氧化酮类或醛类有机化合物,合成相应的肟类化合物。本发明与现有技术相比具有开放的孔道结构,氨氧化性能、使用寿命及催化稳定性均显著提高,酮类或醛类反应物的转化率和目标产物选择性均接近99%或更高,拓宽了酮类氨氧化催化反应的研究和应用领域。
Description
技术领域
本发明涉及无机化学合成和化工应用技术领域,具体的说是一种ECNU-29新型钛铝硅酸盐纳米片催化剂及其制备方法和该催化剂在酮类或醛类氨氧化反应中合成肟的应用。
背景技术
肟类化学品是一类重要的化工中间体,以大宗化学品环己酮肟为例,经贝克曼重排可制备ε-己内酰胺,己内酰胺经聚合后可进一步用于合成纤维、塑料、薄膜、人造革等具有巨大的市场需求。以具有有序微孔结构的钛硅酸盐为催化剂、双氧水为氧化剂的液相氧化反应体系制肟类化学品具有反应条件温和、原子利用率高、副产物为水、对环境友好等优点,切合可持续发展的理念,是绿色化学的典型代表。由于催化剂骨架中含具有氧化-还原催化的特性过渡金属钛原子以及孔材料自身的具有的产物择形性,使其具有优异的定向催化氧化性能。
意大利Enichem公司采用钛硅酸盐TS-1为催化剂,以环己酮、过氧化氢、氨水为原料一步合成环己酮肟取得了很好的结果,并实现了工业化应用(Sci.Catal.,1990,55,43.)。继TS-1之后,科技工作者们又相继成功合成了TS-2、Ti-Beta、Ti-MWW等二十多种具有不同拓扑结构的微孔钛硅酸盐材料。钛硅酸盐材料由于具有优异的酮类或醛类氨氧化性能,因此研发具有新结构的钛硅酸盐材料一直是该领域的研究热点;其中采用新型有机模板剂导向合成新型钛硅酸盐材料是一种重要的方法。
发明内容
本发明的目的是针对现有技术的不足而提供的一种ECNU-29钛铝硅酸盐纳米片及其制备方法和应用,采用氧化钛、氧化铝和氧化硅以四面体形式相互连接,构成具有完整晶态结构的ECNU-29钛铝硅酸盐纳米片,该晶态结构以ECNU-29为骨架,且氧化物以四面体形式相互连接构成的一种新型的二维有序微孔复合氧化物材料,其制备是以含苄基的两亲性双季胺盐作为有机模板剂,通过水热合成和铵交换后焙烧,制得具有完整晶态结构的ECNU-29钛铝硅酸盐纳米片,并用于酮类或醛类氨氧化反应中的催化剂,该催化剂具有开放的孔道结构,适于在含有质子性溶剂的体系中催化氧化酮类或醛类有机化合物,合成相应的肟类化合物,氨氧化性能、使用寿命及催化稳定性均得到明显提高,酮类或醛类反应物的转化率和目标产物选择性均接近99%或更高,反应条件温和,反应过程环境友好,进一步拓宽了酮类氨氧化催化反应的研究和应用领域。
本发明的目的是这样实现的:一种ECNU-29钛铝硅酸盐纳米片,其特点是由氧化钛、氧化铝和氧化硅以四面体形式相互连接,构成具有完整晶态结构的有序微孔材料为ECNU-29钛铝硅酸盐纳米片,其化学组成为:TipMm n+AlxSiOy;其中,p为Ti与Si的摩尔比,其变化范围在1/200~1/10间;M为钾离子、钠离子、钙离子、镁离子、氢离子中的一种或两种以上的混合;m为Mn+与Si的摩尔比,其变化范围在1/100~1/5之间;x为Al与Si的摩尔比,其变化范围在1/500~1/5之间;y为O与Si的摩尔比,且y=(4×p+m×n+3×x+4)/2。
表1ECNU-29钛铝硅酸盐的X-射线衍射结构数据表
表中:(a)为粉末X射线衍射谱图中衍射峰的相对强度等级,W为弱级衍射峰;M为中等级衍射峰;S为强级衍射峰;VS为最强级衍射峰;衍射峰强度的最大值定为100,最强级的衍射峰值为60~100,强级的衍射峰值为45~60,中等级的衍射峰值为18~45,弱级的衍射峰值小于18。
本发明的目的之二是提供一种ECNU-29钛铝硅酸盐纳米片的制备方法,其特点是以含苄基的两亲性双季胺盐作为有机模板剂,通过水热合成和铵交换后焙烧,制得具有完整晶态结构的ECNU-29钛铝硅酸盐纳米片,具体制备包括下述步骤:
步骤一:将钛源(以TiO2计)、铝源(以Al2O3计)、碱源(以Mm n+O计)、有机模板剂和水按1.0:0.05~2:0.1~20:0.1~20:200~4000的摩尔比混合,在常温下搅拌0.5~24小时,直至得到澄清透明的混合溶液。所述钛源六氟钛酸、钛酸四丁酯、硫酸钛或硝酸钛中的一种或两种以上的混合;所述铝源为偏铝酸钠、硫酸铝、异丙醇铝、硝酸铝或氢氧化铝中的一种或两种以上的混合;所述碱源为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾和碳酸氢钠中的一种或两种以上的混合。
步骤二:将硅源(以SiO2计)加入到步骤一得到的混合溶液中,在25~100℃温度下搅拌0.5~24小时,得到的混合凝胶,其组成以摩尔比表示为TiO2:Al2O3:Mm n+O:有机模板剂:SiO2:H2O为1.0:0.05~2:0.1~20:0.1~20:10~200:200~4000;所述硅源为硅溶胶、硅酸、发烟硅胶和硅酸四烷基酯中的一种或两种以上的混合。
步骤三:将步骤二所得混合凝胶在130~200℃温度下进行7~30天水热晶化反应,晶化后的反应液经过滤、洗涤、干燥和焙烧,得产物为非氢型的ECNU-29钛铝硅酸盐纳米片。
步骤四:将步骤三得到的非氢型ECNU-29钛铝硅酸盐纳米片与铵盐溶液按1:10~100的重量比混合,于60~150℃温度下反应0.5~10小时,其反应液经过滤、洗涤、干燥和焙烧,制得氢型ECNU-29钛铝硅酸盐纳米片,所述铵盐为氟化铵、氯化铵、硫酸铵和硝酸铵中的一种或两种以上的混合;所述铵盐溶液为铵盐的水溶液或甲醇溶液,其浓度为0.1~2M。
所述有机模板剂为含苄基的两亲性双季胺盐,其结构如下:
该有机结构导向剂为带两个正电荷的苄基双季胺盐结构,R1表示含有3~10个碳原子的烷基链,优选3~6;R2表示含有1~20个碳原子的烷基链,优选10~18,Z为有机结构导向剂的抗衡阴离子,为F-、Cl-、Br-、I-或OH-中。
所述步骤一中混合溶液的钛源(以TiO2计)、铝源(以Al2O3计)、碱源(以Mm n+O计)、有机模板剂和水的优选摩尔比为1.0:0.1~0.5:2~8:2~8:1000~3000,优选处理条件为常温下搅拌1~3小时。
所述步骤二中混合凝胶的TiO2:Al2O3:Mm n+O:有机模板剂:SiO2:H2O的优选摩尔比为1.0:0.1~0.5:2~8:2~8:30~70:1000~3000,优选处理条件为70~90℃温度下搅拌8~15小时。
所述步骤三中水热晶化的优选温度为150~180℃。
所述步骤四中制备氢型ECNU-29钛铝硅酸盐纳米片的优选温度为70~90℃,优选处理时间为1~3小时;所述铵盐溶液的优选浓度为0.5~1.5M。
本发明的目的之三是提供以上述制备的氢型ECNU-29钛铝硅酸盐纳米片为催化剂,在酮类或醛类有机物的液相反应中催化合成肟类化合物,其具体应用如下述步骤:
步骤一:依次将催化剂、溶剂、酮或醛类化合物的至少一种、氨、过氧化氢加入到带有冷凝装置的烧瓶中,所述酮或醛类化合物与催化剂和溶剂的重量比为1.0:0.01~0.10:6~50;所述酮或醛类化合物与氨的摩尔比为1.0:0.10~2.0;所述酮或醛类化合物与过氧化氢的摩尔比为1.0:0.10~2.0;所述酮类化合物为碳原子数不大于6的酮,可以但不限于是丙酮、丁酮、环己酮等;所述醛类化合物为碳原子数不大于7的醛,可以但不限于是乙醛、丙醛、丁醛、戊醛、苯甲醛等;所述溶剂为质子性溶剂R-OH,其中R=H或碳原子数为1~4的烷基基团,优选溶剂为R-OH,其中,R=H或C4。
步骤二:将第一步反应液的温度稳定在30~120℃温度以内,磁力搅拌,反应时间为10~120分钟。
步骤三:反应完毕后,按常规过滤方法分离出催化剂,然后按常规操作分离,得到相应的肟产物。
附图说明
图1为实施例1制备的ECNU-29的X射线衍射谱图;
图2为实施例1制备的ECNU-29的扫描电镜图;
图3为实施例1制备的ECNU-29的透射电镜图;
图4为实施例1制备的ECNU-29的孔径分布曲线。
具体实施方式
本发明由氧化钛、氧化铝和氧化硅以四面体形式相互连接,构成具有完整晶态结构的有序微孔材料为ECNU-29钛铝硅酸盐纳米片,其化学组成为:TipMm n+AlxSiOy;其中,p为Ti与Si的摩尔比,其变化范围在1/200~1/10间;M为钾离子、钠离子、钙离子、镁离子、氢离子中的一种或两种以上的混合;m为Mn+与Si的摩尔比,其变化范围在1/100~1/5之间;x为Al与Si的摩尔比,其变化范围在1/500~1/5之间;y为O与Si的摩尔比,且y=(4×p+m×n+3×x+4)/2。
以下通过具体实施例对本发明的制备作进一步的阐述:
实施例1
步骤一:将钛酸四丁酯(以TiO2计)、偏铝酸钠(以Al2O3计)、氢氧化钠(以Na2O计)、有机模板剂(R1选取丁基,R2选取十六烷基,Z选取OH-)和水以1.0:0.25:5:5:2000的摩尔比混合,常温下搅拌2小时,直至得到澄清透明的混合溶液。
步骤二:将8克硅溶胶(以SiO2计)加入到步骤一的混合液中,适当调节水量后在80℃温度下搅拌12小时;所得混合凝胶组成的TiO2:Al2O3:Na2O:有机模板剂:SiO2:H2O的摩尔比为1.0:0.25:5:5:50:2000。
步骤三:将步骤二所得混合凝胶在170℃温度下进行21天水热晶化反应,晶化后的反应液经过滤、洗涤、干燥和焙烧得产物为非氢型的ECNU-29钛铝硅酸盐纳米片。
步骤四:将步骤三得到的非氢型ECNU-29与浓度为1M的氯化铵水溶液按重量比为1:30混合,于80℃温度下处理2小时,其反应液经过滤、洗涤、干燥和焙烧,得产物为氢型ECNU-29钛铝硅酸盐纳米片。
表1 ECNU-29钛铝硅酸盐的X-射线衍射结构数据表
上述表中的(a)为粉末X射线衍射谱图中衍射峰的相对强度等级,W为弱级衍射峰;M为中等级衍射峰;S为强级衍射峰;VS为最强级衍射峰;衍射峰强度的最大值定为100,最强级的衍射峰值为60~100,强级的衍射峰值为45~60,中等级的衍射峰值为18~45,弱级的衍射峰值小于18。
参阅附图2,实施例1制备的氢型ECNU-29钛铝硅酸盐纳米片经扫描电镜显示为花瓣状片层结构形貌。
参阅附图3,实施例1制备的氢型ECNU-29钛铝硅酸盐纳米片经透射电镜显示为堆叠的二维片层结构。
参阅附图4,实施例1制备的氢型ECNU-29钛铝硅酸盐纳米片由Ar吸附曲线计算得到的孔径分布曲线表明:具有有序微孔结构,孔径在0.6纳米左右。
以下将实施例1制备的氢型ECNU-29钛铝硅酸盐纳米片作为用于酮类有机物合成肟的催化剂,对本发明的应用作进一步的阐述:
实施例2
步骤一:依次将催化剂、水、丙酮、氨、过氧化氢加到带有冷凝装置的烧瓶中混合为反应液,所述丙酮与催化剂和水的重量比为1.0:0.05:15;所述氨与丙酮的摩尔比为1:1.5;所述丙酮与过氧化氢的摩尔比为1:1.2。
步骤二:将步骤一反应液的温度稳定在60℃温度,磁力搅拌,反应1小时。
步骤三:反应完毕后,按常规过滤方法分离出催化剂,然后按常规操作分离得产物为丙酮肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,丙酮转化率为99.6%,丙酮肟选择性为99.1%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表2:
表2 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
丙酮转化率(%) | 丙酮肟选择性(%) | |
实施例2 | 99.6 | 99.1 |
对比例1 | 73.5 | 89.2 |
上述对比例1中的催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件均与实施例2相同,通过实施例2与对比例1的气相色谱分析表明,本发明制备的ECNU-29钛铝硅酸盐纳米片在丙酮氨氧化反应中的催化活性明显提高。
实施例3
除酮类化合物为丁酮外,其余均同实施例2,所述丁酮与催化剂和水的重量比为1.0:0.05:12,所述丁酮与氨的摩尔比为1:1.5;所述丁酮与过氧化氢的摩尔比为1:1.2,得产物为丁酮肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,丁酮转化率为99.5%,丁酮肟选择性为99.3%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表3:
表3 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
丁酮转化率(%) | 丁酮肟选择性(%) | |
实施例3 | 99.5 | 99.3 |
对比例2 | 70.7 | 91.6 |
上述对比例2中的催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件均与实施例3相同,通过实施例3与对比例2的气相色谱分析表明,本发明方法制备的钛铝硅酸盐ECNU-29纳米片在丁酮氨氧化反应中的催化活性明显提高。
实施例4
除酮类化合物为丁酮外,其余均同实施例2,所述环己酮与催化剂和水的重量比为1.0:0.05:10,所述环己酮与氨的摩尔比为1:1.5,所述环己酮与过氧化氢的摩尔比为1:1.2,得产物为环己酮肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,环己酮转化率为99.6%,环己酮肟选择性为99.4%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表4:
表4 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
环己酮转化率(%) | 环己酮肟选择性(%) | |
实施例4 | 99.6 | 99.4 |
对比例3 | 66.3 | 82.7 |
上述对比例3中的催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件与实施例4相同,通过实施例4与对比例3的气相色谱分析表明,本发明方法制备的钛铝硅酸盐ECNU-29纳米片在环己酮氨氧化反应中的催化活性明显提高。
实施例5
除酮类化合物为环己酮,溶剂为正丁醇外(实施例2使用的溶剂为水),其余均同实施例2,所述环己酮与催化剂和正丁醇的重量比为1.0:0.05:20;所述环己酮与氨的摩尔比为1:1.5;所述环己酮与过氧化氢的摩尔比为1:1.2,得产物为环己酮肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,环己酮转化率为99.0%,环己酮肟选择性为99.3%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表5:
表5 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
环己酮转化率(%) | 环己酮肟选择性(%) | |
实施例5 | 99.0 | 99.3 |
对比例4 | 61.8 | 83.7 |
上述对比例4中催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件与实施例5相同,通过实施例5与对比例4的气相色谱分析表明,本发明方法制备的钛铝硅酸盐ECNU-29纳米片在环己酮氨氧化反应中的催化活性明显提高。
以下将实施例1制备的氢型ECNU-29钛铝硅酸盐纳米片作为用于醛类有机物合成肟的催化剂,对本发明的应用作进一步的阐述:
实施例6
除醛类化合物为乙醛外,其余均同实施例2,所述乙醛与催化剂和水的重量比为1.0:0.05:20;所述乙醛与氨的摩尔比为1:1.5;所述乙醛与过氧化氢的摩尔比为1:1.2,得产物为乙醛肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,乙醛转化率为99.3%,乙醛肟选择性为98.9%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表6:
表6 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
乙醛转化率(%) | 乙醛肟选择性(%) | |
实施例6 | 99.3 | 98.9 |
对比例5 | 85.1 | 95.6 |
上述对比例5中催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件与实施例6相同,通过实施例6与对比例5的气相色谱分析表明,本发明方法制备的钛铝硅酸盐ECNU-29纳米片在乙醛氨氧化反应中的催化活性明显提高。
实施例7
除醛类化合物为丁醛外,其余均同实施例2,所述丁醛与催化剂和水的重量比为1.0:0.05:15;所述丁醛与氨的摩尔比为1:1.5;所述丁醛与过氧化氢的摩尔比为1:1.2,得产物为丁醛肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,丁醛转化率为99.2%,丁醛肟选择性为99.3%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表7:
表7 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
丁醛转化率(%) | 丁醛肟选择性(%) | |
实施例7 | 99.2 | 99.3 |
对比例6 | 82.6 | 93.8 |
上述对比例6中催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件与实施例7相同;通过实施例7与对比例的气相色谱分析表明,本发明方法制备的钛铝硅酸盐ECNU-29纳米片在丁醛氨氧化反应中的催化活性明显提高。
实施例8
除醛类化合物为丁醛,溶剂为正丁醇外(实施例2使用的溶剂为水),其余均同实施例2,所述丁醛与催化剂和正丁醇的重量比为1.0:0.05:30;所述丁醛与氨的摩尔比为1:1.5;所述丁醛与过氧化氢的摩尔比为1:1.2,得产物为丁醛肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,丁醛转化率为99.3%,丁醛肟选择性为99.5%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表8:
表8 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
丁醛转化率(%) | 丁醛肟选择性(%) | |
实施例8 | 99.3 | 99.5 |
对比例7 | 80.4 | 94.1 |
上述对比例7中催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件与实施例8相同;通过实施例8与对比例的气相色谱分析表明,本发明方法制备的钛铝硅酸盐ECNU-29纳米片在丁醛氨氧化反应中的催化活性明显提高。
实施例9
除醛类化合物为苯甲醛外,其余均同实施例2,所述苯甲醛与催化剂和水的重量比为1.0:0.05:15;所述苯甲醛与氨的摩尔比为1:1.5;所述苯甲醛与过氧化氢的摩尔比为1:1.2,得产物为苯甲醛肟。
上述产物经气相色谱(Shimadzu-14B,FID)分析,苯甲醛转化率为98.6%,丁醛肟选择性为99.2%,ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较见下表9:
表9 ECNU-29钛铝硅酸盐与TS-1钛硅酸盐的催化活性比较
苯甲醛转化率(%) | 苯甲醛肟选择性(%) | |
实施例9 | 98.6 | 99.2 |
对比例8 | 62.5 | 64.9 |
上述对比例8中催化剂是按照文献(J.Catal.,1991,129,159.)方法合成的TS-1钛硅酸盐,SiO2/TiO2摩尔比为50,其反应条件与实施例9相同;通过实施例9与对比例的气相色谱分析表明,本发明方法制备的钛铝硅酸盐ECNU-29纳米片在苯甲醛氨氧化反应中的催化活性明显提高。
本发明的保护内容不局限于以上实施例,在不背离发明构思的精神和范围下,本领域技术人员能够想到的变化和优点都被包括在本发明中,并且以所附的权利要求书为保护范围。
Claims (4)
1.一种ECNU-29钛铝硅酸盐纳米片,其特征在于由氧化钛、氧化铝和氧化硅以四面体形式相互连接,构成具有完整晶态结构的有序微孔材料为ECNU-29钛铝硅酸盐纳米片,其化学组成为:TipMm n+AlxSiOy;其中,p为Ti与Si的摩尔比,其变化范围在1/200~1/10间;M为钾离子、钠离子、钙离子、镁离子、氢离子中的一种或两种以上的混合;m为Mn+与Si的摩尔比,其变化范围在1/100~1/5之间;x为Al与Si的摩尔比,其变化范围在1/500~1/5之间;y为O与Si的摩尔比,且y=(4×p+m×n+3×x+4)/2。
3.一种权利要求1所述ECNU-29钛铝硅酸盐纳米片的制备方法,其特征在于以含苄基的两亲性双季胺盐为有机模板剂,通过水热合成和铵交换后焙烧,制得具有完整晶态结构的ECNU-29钛铝硅酸盐纳米片,具体制备包括下述步骤:
步骤一:将以TiO2计的钛源与以Al2O3计的铝源、以Mm n+O计的碱源、有机模板剂和水按照1.0∶0.05~2∶0.1~20∶0.1~20∶200~4000摩尔比混合,常温下搅拌0.5~24小时为混合溶液待用,所述钛源为六氟钛酸、钛酸四丁酯、硫酸钛、硝酸钛中的一种或两种以上的混合;所述铝源为偏铝酸钠、硫酸铝、异丙醇铝、硝酸铝、氢氧化铝中的一种或两种以上的混合;所述碱源为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠中的一种或两种以上的混合;所述有机模板剂为含苄基的两亲性双季胺盐的有机结构导向剂,其结构如下:
其中:R1为含有3~10个碳原子的烷基链;R2为含有1~20个碳原子的烷基链;Z为有机结构导向剂的抗衡阴离子,具体为F-、Cl-、Br-、I-或OH-;
步骤二:将以SiO2计的硅源加入上述混合溶液中,在25~100℃温度下搅拌反应0.5~24小时,制得以TiO2计的钛源与以Al2O3计的铝源、以Mm n+O计的碱源、有机模板剂、以SiO2计的硅源和水的摩尔比为1.0∶0.05~2∶0.1~20∶0.1~20∶10~200∶200~4000的混合凝胶,所述硅源为硅溶胶、硅酸、发烟硅胶、硅酸四烷基酯中的一种或两种以上的混合;
步骤三:将上述混合凝胶在130~200℃温度下水热晶化反应7~30天,其反应液经过滤、洗涤、干燥和焙烧,得产物为非氢型ECNU-29钛铝硅酸盐纳米片;
步骤四:将上述非氢型ECNU-29钛铝硅酸盐纳米片与铵盐溶液按1:10~100重量比混合,在60~150℃温度下反应0.5~10小时,其反应液经过滤、洗涤、干燥和焙烧,得产物为氢型ECNU-29钛铝硅酸盐纳米片;所述铵盐为氟化铵、氯化铵、硫酸铵、硝酸铵中的一种或两种以上的混合;所述铵盐溶液为铵盐的水溶液或甲醇溶液,其浓度为0.1~2M。
4.一种权利要求1所述ECNU-29钛铝硅酸盐纳米片的应用,其特征在于将氢型ECNU-29钛铝硅酸盐纳米片用于酮类或醛类氨氧化反应中的催化剂进行合成肟类化合物的催化反应,所述酮类或醛类氨氧化反应是将酮类或醛类有机化合物与催化剂、溶剂、氨和过氧化氢按1.0∶0.01~0.10∶6~50∶0.01~1.0∶0.10~2.0的重量比混合,然后在30~120℃温度下搅拌10~120分钟进行肟化反应,反应结束后滤出催化剂,其滤液经分离、提纯,得产物为肟类化合物,所述酮类有机化合物为碳原子数不大于6的酮类化合物;所述醛类有机化合物为碳原子数不大于7的醛类化合物;所述溶剂为质子性溶剂R-OH,其中R=H或C1~4的烷基基团。
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