CN108014847B - Cu-SSZ-13/SAPO-11 composite structure molecular sieve and synthetic method thereof - Google Patents
Cu-SSZ-13/SAPO-11 composite structure molecular sieve and synthetic method thereof Download PDFInfo
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- CN108014847B CN108014847B CN201610968985.6A CN201610968985A CN108014847B CN 108014847 B CN108014847 B CN 108014847B CN 201610968985 A CN201610968985 A CN 201610968985A CN 108014847 B CN108014847 B CN 108014847B
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- molecular sieve
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- sapo
- ssz
- composite structure
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 136
- 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 136
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000010189 synthetic method Methods 0.000 title claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 21
- -1 copper amine Chemical class 0.000 claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- FWVCSXWHVOOTFJ-UHFFFAOYSA-N 1-(2-chloroethylsulfanyl)-2-[2-(2-chloroethylsulfanyl)ethoxy]ethane Chemical compound ClCCSCCOCCSCCCl FWVCSXWHVOOTFJ-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 18
- 239000010457 zeolite Substances 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000012258 stirred mixture Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910001868 water Inorganic materials 0.000 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 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 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 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 229910052676 chabazite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 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 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 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
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to a Cu-SSZ-13/SAPO-11 composite structure molecular sieve and a synthesis method thereof, which mainly solve the technical problems of single structure, less total amount of strong and weak acid centers and low catalytic activity of a molecular sieve porous material in the prior art, and the invention adopts a Cu-SSZ-13/SAPO-11 composite structure molecular sieve which is characterized in that the Cu-SSZ-13/SAPO-11 composite structure molecular sieve has two phases of Cu-SSZ-13 and SAPO-11, and the XRD diffraction pattern of the molecular sieve has diffraction patterns at 2 theta of 8.09 +/-0.05, 12.92 +/-0.05, 14.01 +/-0.05, 15.75 +/-0.1, 16.05 +/-0.02, 17.89 +/-0.05, 20.25 +/-0.05, 22.66 +/-0.1, 23.24 +/-0.1, 25.06 +/-0.01, 26.32 +/-0.1, 30.73 +/-0.1, 34.53 +/-0.05, 37.73 +/-0.05, 37.43.1, 13 +/-0.1, and better diffraction peaks appear at the positions of the technical scheme, the composite structure molecular sieve can be used in the industrial production of downstream products of methanol.
Description
Technical Field
The invention relates to a Cu-SSZ-13/SAPO-11 composite structure molecular sieve and a synthesis method thereof.
Background
Due to the wide distribution range of the sizes of the inner cavities and the rich diversity of topological structures, the zeolite molecular sieve material is widely applied to the fields of adsorption, heterogeneous catalysis, carriers of various guest molecules, ion exchange and the like. They are mainly characterized by selective adsorption and their unique system of channels gives them the ability to screen molecules of different sizes, which is why these materials are called "molecular sieves". According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), porous materials can be classified into the following three classes according to their pore diameters: the material with the pore diameter less than 2nm is microporous material; the material with the pore diameter between 2 and 50nm is mesoporous material (mesoporous materials); materials with pore sizes greater than 50nm are macroporous materials (macroporous materials) and zeolite molecular sieve channels are typically below 2nm in diameter and are therefore classified as microporous materials.
Early zeolites were aluminosilicates which were made of SiO4Tetrahedron and AlO4Tetrahedron is a basic structural unit and is connected by bridge oxygen to form a microporous compound with a cage-shaped or pore canal structure. In the last 40 th century, Barrer and others synthesized artificial zeolite which did not exist in nature for the first time in the laboratory, and in the next more than ten years, Milton, Breck and Sand and others synthesized A-type, X-type, L-type and Y-type zeolites, mordenite and the like by adding alkali metal or alkaline earth metal hydroxide to aluminosilicate gel by using a hydrothermal technology;
in the sixties of the twentieth century, along with the introduction of organic base cations, a series of zeolite molecular sieves with brand new structures, such as ZSM-n series (ZSM-1, ZSM-5, ZSM-11, ZSM-22, ZSM-48 and the like) zeolite molecular sieves, are prepared, and have the advantages of good catalytic activity, good hydrothermal stability, high corrosion resistance and the like, so that the zeolite molecular sieves are widely applied to the fields of petroleum processing, fine chemical engineering and the like and are the hot spots of research of people for many years.
In the eighties of the twentieth century, the chemist of chevrong corporation, Zones S.I., synthesized a new molecular sieve SSZ-13 (U.S. Pat. No.4544538) under the condition of N, N, N-trimethyl-1-adamantanamine (TMAA +) organic cation as a structure directing agent. The zeolite is a Chabazite (CHA) having a structure made of AlO4And SiO4The tetrahedron is connected end to end through oxygen atoms and is orderly arranged into an ellipsoidal crystal structure with an eight-membered ring structure, the size of a pore channel is only 0.3nm, the tetrahedron is divided according to the size of the pore channel of the zeolite, SSZ-13 belongs to small-pore zeolite, and the specific surface area can reach 700m at most2(ii) in terms of/g. Due to the large specific surface area and the structural characteristics of eight-membered ring, SSZ-13 has good thermal stability and can be used as adsorbent or catalystCarriers for agents such as air purifiers, automotive exhaust catalysts, and the like. Meanwhile, SSZ-13 also has cation exchange property and acidity adjustability, so that the catalyst has good catalytic performance on various reaction processes, including catalytic cracking and hydrocracking of hydrocarbon compounds, olefin and aromatic hydrocarbon structural reaction and the like. However, the relatively expensive structure directing agents used make the synthesis of SSZ-13 molecular sieves cost prohibitive, and consequently limit the use of molecular sieve SSZ-13 in commercial production.
It is mentioned in the specification of patent No.60826882 filed on Zones s s.i. 25.2006, 9, he found a method to reduce the dosage of TMAA + used as a structure directing agent for the synthesis of SSZ-13 molecular sieves. The dosage of TMAA + cation can be significantly reduced by adding benzyl quaternary ammonium ion and TMAA + cation together as a structure directing agent for the reactants. While this synthesis approach is effective in reducing cost, it still uses expensive TMAA + cations.
A method of synthesizing SSZ-13 molecular sieves using benzyltrimethyl quaternary ammonium ions (BzTMA +) as a partial replacement for N, N-trimethyl-1-amantadine cations as structure directing agents is proposed in the application specification of patent No.60882010 filed by Miller, 27.2006.
Although the price of benzyltrimethyl quaternary ammonium ion is relatively low, benzyltrimethyl quaternary ammonium ion is not the most suitable structure directing agent because it is irritating and harmful to human body. With the continuous expansion of the application field of zeolite and the need of scientific research development for new properties and new performances, a great deal of effort is put into the synthesis and preparation of novel zeolite molecular sieves, wherein, the use of heteroatoms (metal elements with heavier atomic weight) to replace framework elements for preparing zeolite molecular sieves with novel framework structures and specific properties becomes one of the effective synthesis and preparation modes of novel zeolite molecular sieves.
The method (Chin.J.Catal.,2012,33: 92-105) for preparing Cu-SSZ13 in situ by using a Cu complex as an organic template is reported by Shokushou et al in 2012, and in the method, tetraethylenepentamine is used as a complexing agent to be complexed with copper ions to form Cu-TEPA as the organic template, so that the Cu-SSZ-13 molecular sieve with higher crystallinity and purity can be prepared under the condition of not using TMAA + as the template.
SAPO-11, as an important member of silicoaluminophosphate series molecular sieves (SAPO-n, n stands for the type) developed by United states carbide corporation (UCC) in the eighties of the last century, has unique one-dimensional ten-membered ring straight channel (0.39nm multiplied by 0.63nm) and has a topological structure of MEL. In the structure of SAPO-n, Si atom replaces P or Al atom in original AlPO to form SiO4、AlO4And PO4A non-neutral molecular sieve framework of tetrahedral composition, in which silicon is present in two ways: (1) one Si atom replacing one P atom; (2)2 silicon atoms replace a pair of aluminum and phosphorus atoms, respectively.
The traditional method for preparing the SAPO-11 molecular sieve is a hydrothermal synthesis method, such as U.S. patents USP4440871, USP4701485, USP4943424 and the like, a reactant aluminum source is aluminum isopropoxide or pseudo-boehmite, a phosphorus source is phosphoric acid, a silicon source is commonly used as acidic silica sol, and commonly used templates are di-n-propylamine and diisopropylamine, so that the method has the defects of difficult repetition, more formed Si regions and the like, and is not beneficial to the application of the SAPO-11.
Chinese patents 00129373.7 and 200910081007.0 report that organic alcohol is used in the reactants to prepare SAPO-11 molecular sieve with small particle size and high cleanliness.
At present, no report is found on the Cu-SSZ-13/SAPO-11 composite structure molecular sieve and a synthetic method thereof.
Disclosure of Invention
The invention provides a Cu-SSZ-13/SAPO-11 composite structure molecular sieve, which aims to solve the technical problems of single structure, less total amount of strong and weak acid centers and low catalytic activity of a molecular sieve porous material and has the advantages of complex pore structure distribution, more total amount of strong and weak acid centers and high catalytic activity.
The second technical problem to be solved by the invention is that the prior art does not relate to the synthesis method of the molecular sieve with the Cu-SSZ-13/SAPO-11 composite structure, and provides a novel preparation method of the molecular sieve with the Cu-SSZ-13/SAPO-11 composite structure.
The invention aims to solve the technical problem of providing the application of the Cu-SSZ-13/SAPO-11 composite structure molecular sieve in preparing downstream products of methanol.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the Cu-SSZ-13/SAPO-11 composite structure molecular sieve is characterized in that the Cu-SSZ-13/SAPO-11 composite structure molecular sieve has two phases of Cu-SSZ-13 and SAPO-11, wherein the weight percentage of the Cu-SSZ-13 molecular sieve is 1-99%; the weight percentage content of the SAPO-11 molecular sieve is 1-99%, and the XRD diffraction pattern of the SAPO-11 molecular sieve has diffraction peaks at the positions of 8.09 +/-0.05, 9.53 +/-0.02, 12.92 +/-0.05, 13.07 +/-0.1, 14.01 +/-0.05, 15.75 +/-0.1, 16.05 +/-0.02, 17.89 +/-0.05, 20.25 +/-0.05, 20.65 +/-0.05, 21.21 +/-0.01, 22.66 +/-0.1, 23.24 +/-0.1, 25.06 +/-0.01, 26.01 +/-0.02, 27.94 +/-0.1, 26.32 +/-0.1, 30.73 +/-0.1, 31.73 +/-0.02, 32.73 +/-0.05, 34.53 +/-0.05, 37.73 +/-0.1 and 43.13 +/-0.1 of 2 theta.
In the technical scheme, preferably, the Cu-SSZ-13 molecular sieve in the composite structure molecular sieve accounts for 5-95% by weight of the Cu-SSZ-13/SAPO-11 composite structure molecular sieve; the weight percentage content of the SAPO-11 molecular sieve is 5-95%.
In the technical scheme, more preferably, the Cu-SSZ-13 molecular sieve in the composite structure molecular sieve accounts for 30-75% by weight of the Cu-SSZ-13/SAPO-11 composite structure molecular sieve; the weight percentage content of the SAPO-11 molecular sieve is 25-70%.
To solve the second technical problem, the invention adopts the following technical scheme: a synthetic method of a Cu-SSZ-13/SAPO-11 composite structure molecular sieve comprises the following steps:
a. firstly, mixing an aluminum source and a solvent to form a solution S, and dividing the solution into two parts to be marked as the solution S1And solution S2；
b. Adding a portion of the silicon source, copper salt, chelating agent and/or copper amine chelate to S1Fully stirring the medium solution for 0.5-5 h, and adding an inorganic base to adjust the pH value of the system to 8-12 during stirring to obtain a solution S1’；
c. Adding the rest silicon source, phosphorus source and organic template agent required for synthesizing SAPO-11 molecular sieve into S2Stirring the solution for 0.5 to 5 hours to obtain solution S2’；
d. Mixing the solution S1' with solution S2Respectively placing the solution S at 80-120 ℃ for pre-crystallization treatment for 0.5-5 h, and then carrying out the solution S1' with solution S2Uniformly mixing, and stirring for 1-10 h in a closed manner at the temperature of 80-120 ℃ to form a uniform crystallized mixture;
e. and d, crystallizing the crystallized mixture obtained in the step d at 100-200 ℃ for 5-168 hours, filtering and washing the product, drying the product at 80-120 ℃, heating to 400-650 ℃, and roasting at constant temperature for 4-12 hours.
In the above technical solution, preferably, the molar ratio of the raw materials used is: n (Si/Al) is 1 to infinity, n (P/Al) is 0.01 to 1000, n (templating agent T/Al) is 1 to 5000, n (solvent S/Al) is 10 to 10000, and n (OH/Al) is 1 to 1000.
In the above technical solution, preferably, the molar ratio of the raw materials used is: n (Si/Al) is 1-500, n (P/Al) is 0.1-100, n (template agent T/Al) is 10-1000, n (solvent S/Al) is 100-5000, and n (OH/Al) is 1-500; solution S in step a1And solution S2The weight ratio of (A) to (B) is 0.1-10: 1; and the silicon source used in the step b accounts for 5-95% of the total silicon source by mass.
In the above technical solution, more preferably, the molar ratio of the raw materials used is: n (Si/Al) is 1-200, n (P/Al) is 0.5-50, n (template agent T/Al) is 20-200, n (solvent S/Al) is 200-600, and n (OH/Al) is 3-50; solution S in step a1And solution S2The weight ratio of (A) to (B) is 0.2-5: 1; and the silicon source used in the step b accounts for 15-85% of the total silicon source by mass percent.
In the above embodiment, the aluminum source is preferably at least one selected from the group consisting of aluminates, meta-aluminates, hydroxides of aluminum, oxides of aluminum, and minerals containing aluminum; the copper source is selected from at least one of halogen compounds, nitrate, sulfate and acetate of copper; the silicon source is at least one of organic silicon, amorphous silica, silica sol, solid silica, silica gel, diatomite or water glass; the phosphorus source is at least one of orthophosphoric acid, ammonium monohydrogen phosphate or diammonium hydrogen phosphate; the inorganic base is at least one of hydroxides of alkali metals or alkaline earth metals.
In the above technical solution, preferably, the aluminum source is at least one selected from aluminates and meta-aluminates; the silicon source is at least one of amorphous silica, silica sol or solid silica; the phosphorus source is at least one of orthophosphoric acid and ammonium monohydrogen phosphate; the inorganic base is at least one of LiOH, NaOH or KOH.
In the above technical solution, preferably, the template agent required for preparing the Cu-SSZ-13 molecular sieve is a copper salt, a chelating agent and/or a copper amine chelate, wherein the chelating agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1, 10-phenanthroline, 2-bipyridine or 4, 4-bipyridine; the organic template agent required for preparing the SAPO-11 molecular sieve is organic amine and is selected from at least one of tetrapropyl ammonium bromide, tetrapropyl ammonium hydroxide, tetraethyl ammonium bromide, tetraethyl ammonium hydroxide, tetrabutyl ammonium bromide, tetrabutyl ammonium hydroxide, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine or ethylamine; the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, ethanol, ethylene glycol or deionized water.
In the above technical solution, preferably, the chelating agent is at least one selected from diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the solvent is at least one selected from N, N-dimethylformamide, ethanol or deionized water;
in order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the Cu-SSZ-13/SAPO-11 composite structure molecular sieve is used as a catalyst for reactions for preparing hydrocarbons from methanol, hydrogenation reactions and olefin cracking reactions.
In the technical scheme, the use method of the molecular sieve catalyst with the Cu-SSZ-13/SAPO-11 composite structure comprises the following steps: the Cu-SSZ-13/SAPO-11 composite structure molecular sieve catalyst is applied to hydrogenation reaction of unsaturated compounds or macromolecules with unsaturated bonds; more preferably, the catalyst is suitable for use in hydrogenation processes for cracking unsaturated components in hydrocarbon fractions of carbon nine and above.
In the technical scheme, the use method of the molecular sieve catalyst with the Cu-SSZ-13/SAPO-11 composite structure comprises the following steps: the Cu-SSZ-13/SAPO-11 composite structure molecular sieve catalyst is applied to hydrocarbon cracking reaction; preferably, the cracking reaction conditions are as follows: the reaction temperature is 500-650 ℃, the weight ratio of the diluent to the raw material is 0-1: 1, and the liquid phase airspeed is 1-30 h-1The reaction pressure is-0.05 to 0.2 MPa. The hydrocarbon preferably comprises at least one olefin, more preferably at least one C4And the above olefins.
In the technical scheme, the use method of the molecular sieve catalyst with the Cu-SSZ-13/SAPO-11 composite structure comprises the following steps: the application of the molecular sieve catalyst with the Cu-SSZ-13/SAPO-11 composite structure in the reaction of preparing the hydrocarbon from the methanol is disclosed; preferably, the reaction conditions for preparing hydrocarbons by methanol conversion are as follows: methanol is used as a raw material, the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-10 MPa, and the weight space velocity of the methanol is 0.1-15 h-1。
The content of the metal element Cu in the composite structure molecular sieve is determined on a plasma Perkin-Elmer 3300DV ICP analyzer, and the specific operation method is as follows:
placing the sample in an oven at 100 ℃ for drying for 2h, then weighing 0.2-0.5 g of the dried sample in a platinum crucible or a plastic crucible, and adding 10 drops of the mixture in a volume ratio of 1:1, heating the sulfuric acid solution with 8mL of hydrofluoric acid, frequently shaking to accelerate the decomposition of the sample, evaporating the solution until white smoke is exhausted after the solution in the crucible is clear, taking down and cooling, and adding 5mL of hydrochloric acid and a proper amount of water in a volume ratio of 1: 1. Heating to dissolve the residue, transferring into a 100mL volumetric flask, washing the crucible with water, diluting to a scale, shaking up, introducing the prepared solution into an ICP spectrometer for analysis, and recording the percentage content.
The molecular sieve with the composite structure provided by the invention has the characteristics of pore channel structures and acidic characteristics of two molecular sieves, and shows a good synergistic effect. The optimal pore structure and the proper acidity of the composite molecular sieve are obtained by changing the proportion of two phases in the composite molecular sieve through in-situ regulation and optimization of synthesis conditions, the composite molecular sieve is used for the reaction process of preparing hydrocarbon through methanol conversion, the conversion rate of methanol is 100 percent within a set evaluation condition range, the one-way yield of ethylene, propylene and isobutene can reach 75.9 percent at most, and meanwhile, the catalyst has good stability and obtains better technical effects.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Synthesis of Cu-SSZ-13/SAPO-11 composite structure molecular sieve
4121.21g of aluminum nitrate [ Al (NO) were weighed3)3·9H2O, purity is more than or equal to 98 wt.%, 10.98mol]Dissolving in 37366.52mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 60% and 40%, and marking as a solution S1And solution S222101.36g of silica sol [ SiO ]2,40％wt,147.34mol]2166.88g of cupric acetate [ Cu (OAc) ]2·H2O, purity is more than or equal to 98 wt.%, 10.83mol]And 2050.12g of tetraethylenepentamine [ TEPA,10.83mol]Charging S1In the solution, 2200.22g of sodium hydroxide [ NaOH, 55.01mol ] were added under stirring]Adding the solution to adjust the pH value of the solution to be 9-10, and continuously stirring for 5 hours to obtain a solution S1'; 2012.79g of phosphoric acid [ H ]3PO4,85％wt.,17.46mol]2077.05g of acidic silica sol [ SiO ]2，40wt％，13.85mol]And 208.03g of triethylamine [ DEA,2.06mol]Charging S2Stirring the solution for 1 hour to obtain a solution S2'; mixing the solution S1' with solution S2' hydrothermal treatment at 90 ℃ for 18 hours, respectively, after which the solution S was1' with solution S2Uniformly mixing, and stirring for 10 hours in a sealed way at the temperature of 120 ℃; and (3) crystallizing the stirred mixture at 145 ℃ for 15d, filtering and washing the product, drying the product at 110 ℃ for 5h, heating to 400 ℃, and roasting at constant temperature for 12h to obtain a product, namely CZP-1. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: s: OH is 1: 14.68: 1.62: 1.17: 263.99: 5.01, and the content of Cu/SSZ-13 molecular sieve in the CZP-1 molecular sieve is 61.2% and the content of SAPO-11 is 38.8% through ICP test and XRD analysis.
[ example 2 ]
Synthesis of Cu-SSZ-13/SAPO-11 composite structure molecular sieve
3.75g of aluminum nitrate [ Al (NO) was weighed3)3·9H2O, purity is more than or equal to 98 wt.%, 0.01mol]Dissolving in 111.55mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 50% and 50%, and marking as a solution S1And solution S21.21g of white carbon black SiO2,99wt.％,0.02mol]4.82g of copper sulfate [ CuSO ]4·5H2O，0.02mol]And 3.61g of ethylenediamine [ DEA, 0.06mol]Charging S1In the solution, 39.99g of sodium hydroxide [ NaOH, 1.0mol ] was added under stirring]Adding the solution to adjust the pH value of the solution to be 11-12, and continuously stirring for 2.5h to obtain a solution S1'; 10.55g of ammonium dihydrogen phosphate [ NH ]4H2PO4，0.10mol]0.61g of white carbon black SiO2,99wt.％,0.01mol]And 18.35g of ethylenediamine [ EDA,0.30]Charging S2Stirring the solution for 0.5h to obtain a solution S2'; mixing the solution S1' with solution S2' hydrothermal treatment at 80 ℃ for 24 hours, respectively, after which the solution S was1' with solution S2Uniformly mixing, and stirring for 24 hours in a closed manner at 120 ℃; and (3) crystallizing the stirred mixture at 200 ℃ for 5h, filtering and washing the product, drying the product at 80 ℃ for 8h, heating to 550 ℃, and roasting at constant temperature for 9h to obtain a product, namely CZP-2. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: s: the content of Cu/SSZ-13 molecular sieve in the CZP-2 molecular sieve is 52.6 percent and the content of SAPO-11 is 47.4 percent as shown by ICP test and XRD analysis when OH is 1: 3: 10: 32: 10: 6175.
[ example 3 ]
Synthesis of Cu-SSZ-13/SAPO-11 composite structure molecular sieve
2110.55g of aluminum sulfate [ Al ]2(SO4)3·18H2O, purity ≥ 98 wt.%, 3.17mol]Dissolving the mixture in 16322.09mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 40% and 60%, and marking as a solution S1And solution S2997.31g of acidic silica sol [ SiO ]2,40wt.％,6.65mol]1024.35g of Cu-TETA chelate [ prepared from copper salt and triethylene tetramine, 4.97mol, n (Cu: TETA 1:1)]charging S1In the solution, 2506.56g of potassium hydroxide [ Ca (OH) ] was added thereto under sufficient stirring2，44.68mol]Adding the solution to adjust the pH value of the solution to be 10-11, and continuously stirring for 5 hours to obtain a solution S1'; 166.64g of phosphoric acid [ H ]3PO4,85％wt.,1.44mol]1010.18g of acidic silica sol [ SiO ]2,40wt.％,6.73mol]And 2211.38g of tetrabutylammonium bromide [ TPABr,8.31mol]Charging S2Stirring the solution for 1.5h to obtain a solution S2'; mixing the solution S1' with solution S2' hydrothermal treatment at 120 ℃ for 0.5h, respectively, after which the solution S was1' with solution S2Uniformly mixing, and stirring for 0.5h at 120 ℃ in a sealed manner; and (3) crystallizing the stirred mixture at 165 ℃ for 7d, filtering and washing the product, drying the product at 80 ℃ for 9h, heating to 650 ℃, and roasting at constant temperature for 9h to obtain a product, namely CZP-3. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: s: OH is 1: 4.20: 0.45: 1.19: 307.60: 14.09, and the content of Cu/SSZ-13 molecular sieve and SAPO-11 in the CZP-3 molecular sieve is 41.3% and 58.7% respectively through ICP test and XRD analysis.
[ example 4 ]
Synthesis of Cu-SSZ-13/SAPO-11 composite structure molecular sieve
10985.11g of aluminum sulfate [ Al ] were weighed2(SO4)3·18H2O, purity more than or equal to 98 wt.%, 16.50mol]Dissolving the mixture in 35127.55mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 80% and 20%, and marking as a solution S1And solution S29211.36g of white carbon black SiO2,99wt.％,153.52mol]7194.22g of Cu-TEPA chelate [ 28.15mol, n (Cu: TEPA ═ 1:1) from copper salt and tetraethylenepentamine ]]Charging S1In the solution, 22111.66g of lithium hydroxide [ LiOH, 925.49mol ] were added under stirring]Adding the solution to adjust the pH value of the solution to be 11-12, and continuously stirring for 1.5h to obtain a solution S1'; 15332.96g of phosphoric acid [ H ]3PO4,85％wt.,132.99mol]10788.64g of white carbon black SiO2,99wt.％,179.81mol]And 8868.68g of ethylamine [ EA,193.64mol ]]Charging S2Stirring the solution for 12 hours to obtain solution S2'; mixing the solution S1' with solution S2' separately, the solution S was subjected to hydrothermal treatment at 105 ℃ for 6 hours, after which the solution S was1' with solution S2Uniformly mixing, and stirring for 3 hours in a closed manner at 120 ℃; and (2) crystallizing the stirred mixture at 185 ℃ for 3d, filtering and washing the product, drying the product at 110 ℃ for 9h, heating to 650 ℃, and roasting at constant temperature for 10h to obtain a product, namely CZP-4, wherein the stoichiometric ratio of reactants of the system is as follows: al: si: p: t: s: OH is 1: 20.20: 8.06: 13.46: 118.27: 56.09, and ICP test and XRD analysis show that Cu/SSZ-13 molecular sieve content in CZP-3 molecular sieve is 82.1%, and SAPO-11 content is 17.9%.
[ example 5 ]
Synthesis of Cu-SSZ-13/SAPO-11 composite structure molecular sieve
15.75g of sodium aluminate [ NaAlO ] are weighed out2Purity is not less than 98 wt.%, 0.19mol]Dissolving the mixture in 211.98mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 21% and 79%, and marking as a solution S1And solution S260.12g of white carbon black SiO2,99％wt.，1.0mol]118.14g of copper nitrate [ Cu (NO)3)2·3H2O，99％wt.，0.50mol]And 94.65g of tetraethylenepentamine [ TEPA, 0.50mol]Charging S1In the solution, 39.92g of sodium hydroxide [ NaOH, 0.99mol ] were added under stirring]Adding the solution to adjust the pH value of the solution to be 8-9, and continuously stirring for 2.5h to obtain a solution S1'; 131.98g of diammonium hydrogen phosphate [ (NH)4)2HPO4,0.99mol]12.12g of white carbon black SiO2,99％wt.，0.20mol]And 101.16g of di-n-propylamine [ DPA,0.99mol]Charging S2Stirring the solution for 12 hours to obtain solution S2'; mixing the solution S1' with solution S2' separately, the solution S was subjected to hydrothermal treatment at 105 ℃ for 9 hours, after which the solution S was1' with solution S2Uniformly mixing, and stirring for 3 hours in a closed manner at 120 ℃; and (3) crystallizing the stirred mixture at 170 ℃ for 6d, filtering and washing the product, drying the product at 120 ℃ for 6h, heating to 550 ℃, and roasting at constant temperature for 8h to obtain a product, namely CZP-5. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: s: OH 1: 6.23: 5.21ICP test and XRD analysis show that the content of Cu/SSZ-13 molecular sieve in CZP-5 molecular sieve is 23.6%, and the content of SAPO-11 is 76.4%.
[ examples 6 to 20 ]
According to the method of example 5, the raw materials are shown in Table 1, the Cu-SSZ-13/SAPO-11 composite structure molecular sieves are synthesized by controlling different proportions of the reaction materials (Table 2), and the proportions of Cu-SSZ-13 and SAPO-11 in the materials are shown in Table 3.
TABLE 1
TABLE 2
[ example 21 ]
Application of Cu-SSZ-13/SAPO-11 composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The molecular sieve CZP-3 synthesized in example 3 was subjected to ammonium exchange with 4.5 wt% ammonium nitrate solution at 85 deg.C for 2.5 h. And filtering, washing and drying the product at 110 ℃ for 5 hours, then repeatedly carrying out ammonium exchange once, filtering, washing and drying at 110 ℃ for 5 hours, roasting at 550 ℃ for 4 hours to prepare the hydrogen type composite structure molecular sieve, and then tabletting, breaking and screening to obtain 12-20-mesh particles for later use. Methanol is used as a raw material, a fixed bed reactor with the diameter of 15 mm is used, the temperature is 490 ℃, and the mass space velocity is 1.5h-1And the yield of ethylene, propylene and isobutene reaches 75.9 percent under the evaluation of the pressure of 0.55MPa, so that a better technical effect is achieved.
TABLE 3
| Sample numbering | Cu-SSZ-13 content (%) | SAPO-11 content (% by weight) |
| CZP-6 | 61.2 | 38.8 |
| CZP-7 | 99.0 | 1.0 |
| CZP-8 | 1.0 | 99.0 |
| CZP-9 | 75.0 | 25.0 |
| CZP-10 | 64.9 | 35.1 |
| CZP-11 | 78.1 | 21.9 |
| CZP-12 | 90.1 | 9.9 |
| CZP-13 | 55.2 | 44.8 |
| CZP-14 | 95.0 | 5.0 |
| CZP-15 | 88.1 | 11.9 |
| CZP-16 | 60.5 | 39.5 |
| CZP-17 | 75.0 | 25.0 |
| CZP-18 | 30.0 | 70.0 |
| CZP-19 | 99.0 | 1.0 |
| CZP-20 | 5.0 | 95.0 |
[ example 22 ]
The Cu-SSZ-13/SAPO-11 composite structure molecular sieve is applied to the reaction of preparing hydrocarbon by converting methanol.
Harvesting the fruitThe CZP-4 molecular sieve synthesized in example 4 was prepared by the method of example 21, using methanol as raw material, and a fixed bed reactor with a diameter of 15 mm at 400 deg.C and a mass space velocity of 0.1h-1And the yield of ethylene, propylene and isobutene reaches 59.1 percent under the evaluation of the pressure of 0.01MPa, thereby obtaining better technical effect.
[ example 23 ]
Application of Cu-SSZ-13/SAPO-11 composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The catalyst prepared by the catalyst preparation method of the example 21 is taken from the CZP-6 molecular sieve synthesized in the example 6, methanol is taken as raw material, a fixed bed reactor with the diameter of 15 mm is used, and the mass space velocity is 15h at 460 DEG C-1And the yield of ethylene, propylene and isobutene reaches 62.1 percent under the evaluation of the pressure of 10MPa, thereby obtaining better technical effect.
[ example 24 ]
Application of Cu-SSZ-13/SAPO-11 composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The catalyst prepared by the catalyst preparation method of the example 21 is taken from the CZP-16 molecular sieve synthesized in the example 16, methanol is taken as raw material, a fixed bed reactor with the diameter of 15 mm is used, and the mass space velocity is 7.5h at 530 DEG C-1And the yield of ethylene, propylene and isobutene reaches 70.2 percent under the evaluation of the pressure of 4.9MPa, so that a better technical effect is achieved.
[ example 25 ]
Application of Cu-SSZ-13/SAPO-11 composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The catalyst prepared by the catalyst preparation method of example 21 is taken from the CZP-19 molecular sieve synthesized in example 19, methanol is taken as raw material, a fixed bed reactor with the diameter of 15 mm is used, the temperature is 600 ℃, the mass space velocity is 2.6h-1And the pressure is evaluated under the condition of 1.9MPa, the yield of the ethylene, the propylene and the isobutene reaches 68.9 percent, and a better technical effect is obtained.
[ example 26 ]
Application of mechanically mixed Cu-SSZ-13 and SAPO-11 molecular sieve in reaction for preparing hydrocarbon by methanol conversion
Mechanical mixing of the self-made SAPO-11 molecular sieve and the self-made Cu-SSZ-13 molecular sieve at the ratio of the two molecular sieves of example 8 was performed, and the yields of ethylene, propylene and isobutylene reached 56.9% evaluated in the manner of example 21.
[ example 27 ]
Application of mechanically mixed Cu-SSZ-13 and SAPO-11 molecular sieve in reaction for preparing hydrocarbon by methanol conversion
Mechanical mixing of the self-made SAPO-11 molecular sieve and the self-made Cu-SSZ-13 molecular sieve at the ratio of the two molecular sieves of example 11 was performed, and the yields of ethylene, propylene and isobutylene reached 57.1% as evaluated in example 21.
[ example 28 ]
Mechanical mixing of the self-made SAPO-11 molecular sieve and the self-made Cu-SSZ-13 molecular sieve at the ratio of the two molecular sieves of example 5 was performed, and the yields of ethylene, propylene and isobutylene reached 52.6% evaluated in the manner of example 21.
[ COMPARATIVE EXAMPLE 1 ]
The catalyst prepared by the catalyst preparation method of example 21 and taken from the prepared SAPO-11 molecular sieve was evaluated according to the method of example 23, and the yield of ethylene, propylene and isobutylene reached 15.1%.
[ COMPARATIVE EXAMPLE 2 ]
The catalyst prepared by the catalyst preparation method of example 21 was evaluated according to the method of example 23, and the yields of ethylene, propylene and isobutylene reached 40.7%.
[ COMPARATIVE EXAMPLE 3 ]
The catalyst prepared by the catalyst preparation method of example 21 was evaluated according to the method of example 23, and the yields of ethylene, propylene and isobutylene reached 31.3%, using the self-made SSZ-13 molecular sieve.
[ example 29 ]
Application of Cu-SSZ-13/SAPO-11 composite structure molecular sieve in hydrogenation reaction
The catalyst prepared by the method for preparing the catalyst of example 21 is used for catalyzing the CZP-14 molecular sieve synthesized in example 14The agent is reduced for 15 hours at 480 ℃ in pure hydrogen flow of 1.3L/min to obtain the metal type Cu-SSZ-13/SAPO-11 molecular sieve. As the aromatic hydrocarbon in the hydrocarbon fractions of the cracked carbon nine and above accounts for 65-80 percent and simultaneously contains a large amount of polymerizable unsaturated components, the test example selects the raw materials prepared by the hydrocarbon of the cracked carbon nine and above and the saturated hydrogenated oil according to a certain proportion (the specific components are shown in the table 4) to carry out the hydrogenation activity test of the catalyst. The process conditions are as follows: the inlet temperature is 72 ℃, the pressure is 2.2MPa, and the space velocity LHSV of the fresh oil is 2.1h-1Volume ratio of hydrogen to oil H2Raw oil 509: 1, the results are shown in table 4.
TABLE 4
[ COMPARATIVE EXAMPLE 4 ]
Taking Cu/Al2O3-SiO2The hydrogenation activity of the catalyst was measured under the conditions of example 26, and the results are shown in Table 5.
TABLE 5
[ example 27 ]
Application of Cu-SSZ-13/SAPO-11 composite structure molecular sieve in olefin cracking reaction
The catalyst is prepared by selecting the CZP-20 molecular sieve synthesized in the example 20 and adopting the catalyst preparation method of the example 21, and the reaction temperature is 660 ℃, the reaction pressure is 0.03MPa, and the weight space velocity is 1.5h-1The results are shown in Table 6.
[ COMPARATIVE EXAMPLE 5 ]
Taking SiO2/Al2O3Mordenite with a molar ratio of 11, prepared by the method of preparation of the catalyst of example 21The agents were evaluated in the same manner as in example 27, and the results are shown in Table 6.
[ COMPARATIVE EXAMPLE 6 ]
Taking SiO2/Al2O3A catalyst prepared by the method for preparing the catalyst of example 21 was evaluated as in example 27 and the results are shown in Table 6, using zeolite beta in a molar ratio of 35.
[ COMPARATIVE EXAMPLE 7 ]
Taking SiO2/Al2O3A catalyst prepared by the catalyst preparation method of example 21 was evaluated as in example 27 and the results are shown in Table 6, using Y zeolite having a molar ratio of 12.
[ COMPARATIVE EXAMPLE 8 ]
Taking SiO2/Al2O3A catalyst prepared by the catalyst preparation method of example 21 was evaluated in the same manner as in example 27 and the results are shown in Table 6, using a ZSM-5 molecular sieve having a molar ratio of 51.
TABLE 6
Claims (10)
1. The Cu-SSZ-13/SAPO-11 composite structure molecular sieve is characterized in that the Cu-SSZ-13/SAPO-11 composite structure molecular sieve has two phases of Cu-SSZ-13 and SAPO-11, wherein the weight percentage of the Cu-SSZ-13 molecular sieve is 1-99%; the weight percentage content of the SAPO-11 molecular sieve is 1-99%, and the XRD diffraction pattern of the SAPO-11 molecular sieve has diffraction peaks at the positions of 8.09 +/-0.05, 9.53 +/-0.02, 12.92 +/-0.05, 13.07 +/-0.1, 14.01 +/-0.05, 15.75 +/-0.1, 16.05 +/-0.02, 17.89 +/-0.05, 20.25 +/-0.05, 20.65 +/-0.05, 21.21 +/-0.01, 22.66 +/-0.1, 23.24 +/-0.1, 25.06 +/-0.01, 26.01 +/-0.02, 27.94 +/-0.1, 26.32 +/-0.1, 30.73 +/-0.1, 31.73 +/-0.02, 32.73 +/-0.05, 34.53 +/-0.05, 37.73 +/-0.1 and 43.13 +/-0.1 of 2 theta; the Cu-SSZ-13/SAPO-11 composite structure molecular sieve is synthesized by adopting the following method:
the molar ratio of the raw materials used was: n (Si/Al) =1 to infinity, n (P/Al) =0.01 to 1000, n (template agent T/Al) =1 to 5000, n (solvent S/Al) =10 to 10000, n (OH/Al) =1 to 1000, and the synthetic method comprises the following steps:
a. firstly, mixing an aluminum source and a solvent to form a solution, and dividing the solution into two parts to be marked as a solution S1And solution S2；
b. Adding a portion of the silicon source, copper salt, chelating agent and/or copper amine chelate to S1Fully stirring for 0.5-5 h, and adding an inorganic base to adjust the pH value of the system to 8-12 during stirring to obtain a solution S1’；
c. Adding the rest silicon source, phosphorus source and organic template agent required for synthesizing SAPO-11 molecular sieve into S2Stirring the solution for 0.5 to 5 hours to obtain solution S2’；
d. Mixing the solution S1' with solution S2Respectively placing the solution S at 80-120 ℃ for pre-crystallization treatment for 0.5-5 h, and then carrying out the solution S1' with solution S2Uniformly mixing, and stirring for 1-10 h in a closed manner at the temperature of 80-120 ℃ to form a uniform crystallized mixture;
e. and d, crystallizing the crystallized mixture obtained in the step d at 100-200 ℃ for 5-168 hours, filtering and washing the product, drying the product at 80-120 ℃, heating to 400-650 ℃, and roasting at constant temperature for 4-12 hours.
2. The Cu-SSZ-13/SAPO-11 composite structure molecular sieve according to claim 1, wherein the weight percentage of the Cu-SSZ-13 molecular sieve in the composite structure molecular sieve is 5-95% based on the weight percentage of the Cu-SSZ-13/SAPO-11 composite structure molecular sieve; the weight percentage content of the SAPO-11 molecular sieve is 5-95%.
3. The Cu-SSZ-13/SAPO-11 composite structure molecular sieve according to claim 1, wherein the weight percentage of the Cu-SSZ-13 molecular sieve in the composite structure molecular sieve is 30-75%; the weight percentage content of the SAPO-11 molecular sieve is 25-70%.
4. A method for synthesizing a Cu-SSZ-13/SAPO-11 molecular sieve with composite structure according to any of claims 1 to 3, wherein the molar ratio of the raw materials used is: n (Si/Al) =1 to infinity, n (P/Al) =0.01 to 1000, n (template agent T/Al) =1 to 5000, n (solvent S/Al) =10 to 10000, n (OH/Al) =1 to 1000, and the synthetic method comprises the following steps:
a. firstly, mixing an aluminum source and a solvent to form a solution, and dividing the solution into two parts to be marked as a solution S1And solution S2；
b. Adding a portion of the silicon source, copper salt, chelating agent and/or copper amine chelate to S1Fully stirring for 0.5-5 h, and adding an inorganic base to adjust the pH value of the system to 8-12 during stirring to obtain a solution S1’；
c. Adding the rest silicon source, phosphorus source and organic template agent required for synthesizing SAPO-11 molecular sieve into S2Stirring the solution for 0.5 to 5 hours to obtain solution S2’；
d. Mixing the solution S1' with solution S2Respectively placing the solution S at 80-120 ℃ for pre-crystallization treatment for 0.5-5 h, and then carrying out the solution S1' with solution S2Uniformly mixing, and stirring for 1-10 h in a closed manner at the temperature of 80-120 ℃ to form a uniform crystallized mixture;
e. and d, crystallizing the crystallized mixture obtained in the step d at 100-200 ℃ for 5-168 hours, filtering and washing the product, drying the product at 80-120 ℃, heating to 400-650 ℃, and roasting at constant temperature for 4-12 hours.
5. The method for synthesizing the composite structure molecular sieve of claim 4, wherein the molar ratio of the raw materials used is as follows: n (Si/Al) = 1-500, n (P/Al) = 0.1-100, n (template T/Al) = 10-1000, n (solvent S/Al) = 100-5000, n (OH/Al) = 1-500; solution S in step a1And solution S2The weight ratio of (A) to (B) is 0.1-10: 1; and the silicon source used in the step b accounts for 5-95% of the total silicon source by mass.
6. The method for synthesizing the Cu-SSZ-13/SAPO-11 composite structure molecular sieve according to claim 4, wherein the molar ratio of the raw materials is as follows: n (Si/Al) =1 to 200, n (P/Al) =0.5 to 50, n (templating agent T/Al) =20 to 200, n (solvent S/Al) =200 to 600, n: (Si/Al) =1 to 200, n (P/Al) =0.5 to 50, n: (template T/Al) =20 to 200, andOH/Al) = 3-50; solution S in step a1And solution S2The weight ratio of (A) to (B) is 0.2-5: 1; and the silicon source used in the step b accounts for 15-85% of the total silicon source by mass percent.
7. The method for synthesizing the molecular sieve with composite structure according to claim 4, wherein the aluminum source is at least one selected from aluminate, meta-aluminate, aluminum hydroxide, aluminum oxide or aluminum-containing minerals; the copper source is selected from at least one of halogen compounds, nitrate, sulfate and acetate of copper; the silicon source is at least one of organic silicon, amorphous silica, silica sol, silica gel, diatomite or water glass; the phosphorus source is at least one of orthophosphoric acid, ammonium monohydrogen phosphate or diammonium hydrogen phosphate; the inorganic base is at least one of hydroxides of alkali metals or alkaline earth metals.
8. The method for synthesizing the molecular sieve with composite structure according to claim 4, which is used for preparing Cu-SSZ-13
The template agent required by the molecular sieve is copper salt, a chelating agent and/or a copper amine chelate, wherein the chelating agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, 1, 10-phenanthroline, 2-bipyridine or 4, 4-bipyridine; the organic template agent required for preparing the SAPO-11 molecular sieve is organic amine and is selected from at least one of tetrapropyl ammonium bromide, tetrapropyl ammonium hydroxide, tetraethyl ammonium bromide, tetraethyl ammonium hydroxide, tetrabutyl ammonium bromide, tetrabutyl ammonium hydroxide, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine or ethylamine; the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, ethanol, ethylene glycol or deionized water.
9. The method for synthesizing the Cu-SSZ-13/SAPO-11 composite structure molecular sieve according to claim 4, wherein the aluminum source is at least one selected from aluminates and meta-aluminates; the silicon source is at least one of amorphous silica and silica sol; the phosphorus source is at least one of orthophosphoric acid and ammonium monohydrogen phosphate; the inorganic base is at least one of LiOH, NaOH or KOH; the chelating agent is at least one selected from diethylenetriamine, triethylene tetramine and tetraethylene pentamine; the solvent is at least one of N, N-dimethylformamide, ethanol or deionized water.
10. The Cu-SSZ-13/SAPO-11 composite structure molecular sieve as the catalyst of any one of claims 1 to 3, which is used in methanol to hydrocarbon reactions, hydrogenation reactions and olefin cracking reactions.
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