CN108014847A - Cu-SSZ-13/SAPO-11 composite molecular sieves and its synthetic method - Google Patents
Cu-SSZ-13/SAPO-11 composite molecular sieves and its synthetic method Download PDFInfo
- Publication number
- CN108014847A CN108014847A CN201610968985.6A CN201610968985A CN108014847A CN 108014847 A CN108014847 A CN 108014847A CN 201610968985 A CN201610968985 A CN 201610968985A CN 108014847 A CN108014847 A CN 108014847A
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- CN
- China
- Prior art keywords
- molecular sieves
- sapo
- ssz
- solution
- composite molecular
- Prior art date
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- 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 124
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000001228 spectrum Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000010703 silicon Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 19
- 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
- 239000000203 mixture Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- -1 copper amine Chemical class 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical group 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000009415 formwork Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000007787 solid Substances 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 206010013786 Dry skin Diseases 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
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002366 halogen compounds Chemical group 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 241000269350 Anura Species 0.000 abstract 4
- 238000009776 industrial production Methods 0.000 abstract 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 239000010457 zeolite Substances 0.000 description 17
- 229910021536 Zeolite Inorganic materials 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000320 mechanical mixture Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 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
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000003643 water by type 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
- 125000004429 atom Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical group CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 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
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910001431 copper ion 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 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
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 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 present invention relates to a kind of 11 composite molecular sieves of Cu SSZ 13/SAPO and its synthetic method,The structure for mainly solving molecule sieve porous material in the prior art is single,Strong and weak acid site total amount is less,The not high technical problem of catalytic activity,The present invention is by using a kind of 11 composite molecular sieves of Cu SSZ 13/SAPO,It is characterized in that 11 composite molecular sieves of Cu SSZ 13/SAPO have 11 two kinds of thing phases of Cu SSZ 13 and SAPO,Its XRD diffracting spectrum is 8.09 ± 0.05 in 2 θ,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±0.1,Occurs the technical solution of diffraction maximum at 43.13 ± 0.1,Preferably solves the above problem,The composite molecular sieves can be used in the industrial production of Downstream Products of Methanol.
Description
Technical field
The present invention relates to a kind of Cu-SSZ-13/SAPO-11 composite molecular sieves and its synthetic method.
Background technology
Since interior bore size distribution ranges are wide and the rich and varied property of topology, zeolite molecular sieve material are wide
Apply generally in fields such as absorption, heterogeneous catalysis, the carrier of all kinds of guest molecules and ion exchanges.They are with selective absorption
For main feature, its unique pore canal system makes it have the ability for sieving different sized molecules, this is also that this kind of material is claimed
Be " molecular sieve " the reason for.According to international pure and applied chemistry federation (IUPAC) definition, porous material can be by it
Bore dia be divided into following three classes：Material of the aperture less than 2nm is poromerics (micropore materials)；Aperture
It is mesoporous material (mesopore materials) 2 to the material between 50nm；Material of the aperture more than 50nm is macropore material
Expect (macropore materials), zeolite molecular sieve channel diameter is classified as poromerics generally in below 2nm.
Early stage zeolite refers to alumino-silicate, it is by SiO4Tetrahedron and AlO4Tetrahedron is basic structural unit, passes through bridge
One kind that oxygen connects and composes has the containing Microporous Compounds of cage type or pore passage structure.The forties in last century, Barrer etc. are first in reality
Test the artificial zeolite for having synthesized in room and being not present in nature, thereafter into more than ten years, Milton, Breck and Sand etc.
People adds alkali or alkaline earth metal hydroxide using hydrothermal technique in aluminosilicate gels, has synthesized A types, X-type, L-type
With y-type zeolite and modenite etc.；
Nineteen sixties, with the introducing of organic base cation, a series of brand new zeolite molecular sieves are made
It is standby to come out, such as ZSM-n series (ZSM-1, ZSM-5, ZSM-11, ZSM-22, ZSM-48) zeolite molecular sieves, this kind of molecular sieve
There are preferable catalytic activity, hydrothermal stability and higher corrosion resistance, be widely used in PETROLEUM PROCESSING, fine
The fields such as chemical industry, the hot spot that always people study for many years.
The 1980s, the chemist Zones S.I. of Chevron Corporation (Stardard Oil Company of California) are in N, N, N- trimethyl -1- adamantane
Amine (TMAA+) organic cation is as having synthesized a kind of new molecular sieve SSZ-13 (United States Patent (USP) under conditions of structure directing agent
No.4544538).This zeolite is a kind of chabasie (CHA), its structure is by AlO4And SiO4Tetrahedron is first by oxygen atom
Tail connects, and is arranged in the elliposoidal crystal structure with octatomic ring structure in an orderly manner, pore size only has 0.3nm, according to zeolite
Duct size divides, and SSZ-13 belongs to pore zeolite, specific surface area reaches as high as 700m2/g.Since specific surface area is larger simultaneously
Design feature with octatomic ring, SSZ-13 have good heat endurance, can be used as the carrier of adsorbent or catalyst, such as
Air purifying preparation, auto-exhaust catalyst etc..SSZ-13 also has cation exchange and acid adjustability at the same time, thus to more
Kind of reaction process has a good catalytic performance, including hydrocarbon compound catalytic cracking, be hydrocracked and alkene and aromatic hydrocarbons
Construction reaction etc..But cause that the cost of synthesis SSZ-13 molecular sieves is excessive since structure directing agent used is expensive, knot
Fruit limits application of the molecular sieve SSZ-13 in commodity production.
Mentioned in the application specification of the patent No.60826882 of the Zones S.I. applications on the 25th of September in 2006, he looks for
Arrive a kind of reduction and use method of the dosage of TMAA+ as the synthesis SSZ-13 molecular sieves of structure directing agent.By adding benzene
Methyl quaternary ammonium ion and TMAA+ cations can significantly reduce TMAA+ cations together as the structure directing agent of reactant
Dosage.Although this synthetic method effectively reduces cost but used the TMAA+ cations of costliness.
One kind benzyl is proposed in the application specification for the patent No.60882010 that Miller was submitted on December 27th, 2006
Base trimethyl quaternary ammonium ion (BzTMA+) partly replaces N, and N, N- trimethyl -1- amantadine cations are as structure directing agent
The synthetic method of SSZ-13 molecular sieves.
Although the price of benzyl trimethyl quaternary ammonium ion it is relatively low but because it can to human body irritant and certain wound
Evil is so that benzyl trimethyl quaternary ammonium ion can not become most suitable structure directing agent.And as people are to zeolite application field
Constantly widen, and scientific research development is put to new zeolite to the needs of its new property, new capability, substantial amounts of energy
In Zeolite synthesis and preparation work, wherein substituting backbone element using hetero atom (the heavier metallic element of atomic weight) to make
It is standby that there is the zeolite molecular sieve of novel skeleton structure and special properties to become New-type Zeolite Molecular Sieves synthesis with preparing effective means
One of.
Xiao Fengshou in 2012 et al. reports the method that Cu-SSZ13 is prepared in situ using Cu complex compounds as organic template agent
(Chin.J.Catal.,2012,33:92-105), which is complexed to be formed using tetraethylenepentamine as complexing agent with copper ion
Cu-TEPA is organic template agent, and under conditions of without using TMAA+ as template agent, it is higher that crystallinity, purity can be made
Cu-SSZ-13 molecular sieves.
And SAPO-11 develops silicoaluminophosphate series as last century the eighties U.S. combinating carbide company (UCC)
Important a member of molecular sieve (SAPO-n, n represent model), have unique one-dimensional ten-ring straight hole road (0.39nm ×
0.63nm), topology MEL.In the structure of SAPO-n, Si atoms are formed after replacing P the or Al atoms in original AlPO
By SiO4、AlO4And PO4The non-neutral framework of molecular sieve of tetrahedron composition, silicon is with two kinds of sides in the skeleton of this molecular sieve analog
Formula exists：(1) Si atom substitutes a P atom；(2) 2 silicon atoms substitute a pair of of aluminium atom and phosphorus atoms respectively.
The conventional method for preparing SAPO-11 molecular sieves be hydrothermal synthesis method such as United States Patent (USP) USP4440871,
USP4701485, USP4943424 etc., reactant silicon source are aluminium isopropoxide or boehmite, and phosphorus source is phosphoric acid, and silicon source is commonly used
Be acidic silicasol, common template is di-n-propylamine and diisopropylamine, and the above method, which has, to be not easy to repeat, and forms Si areas
The shortcomings of more, is unfavorable for the application of SAPO-11.
Chinese patent 00129373.7,200910081007.0 is reported uses Organic Alcohol in reactant, can prepare
Obtain the high SAPO-11 molecular sieves of small particle, cleanliness factor.
Up to now, the document in relation to Cu-SSZ-13/SAPO-11 composite molecular sieves and its synthetic method is not yet
Appear in the newspapers.
The content of the invention
The first technical problem to be solved by the present invention is that the structure of molecule sieve porous material is single, strong and weak acid site total amount
The not high technical problem of less, catalytic activity, there is provided a kind of Cu-SSZ-13/SAPO-11 composite molecular sieves, the molecular sieve
Has the advantages of pore passage structure complex distribution, strong and weak acid site total amount are more and catalytic activity is higher.
The second technical problem to be solved by the present invention is to be not directed to above-mentioned Cu-SSZ-13/SAPO-11 in the prior art to answer
A kind of the problem of closing structure molecular screen synthetic method, there is provided preparation of new Cu-SSZ-13/SAPO-11 composite molecular sieves
Method.
The third technical problem to be solved by the present invention is to provide a kind of Cu-SSZ-13/SAPO-11 composite molecular sieves
It is used to prepare the purposes of Downstream Products of Methanol.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of Cu-SSZ-13/SAPO-11
Composite molecular sieves, it is characterised in that the Cu-SSZ-13/SAPO-11 composite molecular sieves have Cu-SSZ-13 with
Two kinds of thing phases of SAPO-11, the wherein weight percentage of Cu-SSZ-13 molecular sieves are 1~99%；The weight of SAPO-11 molecular sieves
It is 1~99% to measure percentage composition, its XRD diffracting spectrum is 8.09 ± 0.05,9.53 ± 0.02,12.92 ± 0.05 in 2 θ,
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 ± 0.1,43.13 ±
Occurs diffraction maximum at 0.1.
In above-mentioned technical proposal, it is preferred that with the weight percentage of Cu-SSZ-13/SAPO-11 composite molecular sieves
Count, the weight percentage of Cu-SSZ-13 molecular sieves is 5~95% in the composite molecular sieves；SAPO-11 molecular sieves
Weight percentage be 5~95%.
In above-mentioned technical proposal, it is furthermore preferred that being contained with the weight percent of Cu-SSZ-13/SAPO-11 composite molecular sieves
Gauge, the weight percentage of Cu-SSZ-13 molecular sieves is 30~75% in the composite molecular sieves；SAPO-11 points
The weight percentage of son sieve is 25~70%.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of Cu-SSZ-13/SAPO-11
The synthetic method of composite molecular sieves, comprises the steps of：
A, silicon source and solvent are mixed to form solution S first, then solution is divided into two parts and is denoted as solution S1And solution S2；
B, a part of silicon source, mantoquita, chelating agent and/or copper amine chelate are added into S1It is sufficiently stirred 0.5 in middle solution~
5h, and add inorganic base regulation system pH value in whipping process and solution S is obtained between 8~121’；
C, organic formwork agent needed for remaining silicon source, phosphorus source and synthesis SAPO-11 molecular sieves is added into S2In solution, stir
0.5~5h is mixed, obtains solution S2’；
D, by solution S1' and solution S2' pre- 0.5~5h of Crystallizing treatment at 80~120 DEG C is respectively placed in, afterwards by solution S1’
With solution S2' uniformly mix, 1~10h of closed stirring at 80~120 DEG C, forms uniform crystallization mixture；
E, the crystallization mixture of above-mentioned steps d is placed in 100~200 DEG C, 5~168h of crystallization, product is filtered, after washing
80~120 DEG C of dryings, then heat to 400~650 DEG C, 4~12h of constant temperature calcining.
In above-mentioned technical proposal, it is preferred that raw materials used molar ratio is：N (Si/Al)=1~∞, n (P/Al)=
0.01~1000, n (template T/Al)=1~5000, n (solvent S/Al)=10~10000, n (OH/Al)=1~1000.
In above-mentioned technical proposal, it is preferred that raw materials used molar ratio is：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；Step
Solution S in a1And solution S2Weight ratio be 0.1~10:1；In step b silicon source used account for total silicon source mass percent for 5~
95%.
In above-mentioned technical proposal, it is furthermore preferred that raw materials used molar ratio is：N (Si/Al)=1~200, n (P/Al)
=0.5~50, n (template T/Al)=20~200, n (solvent S/Al)=200~600, n (OH/Al)=3~50；Step a
Middle solution S1And solution S2Weight ratio be 0.2~5:1；In step b silicon source used account for total silicon source mass percent for 15~
85%.
In above-mentioned technical proposal, it is preferred that silicon source is selected from aluminate, meta-aluminate, the hydroxide of aluminium, the oxide of aluminium
Or at least one of mineral containing aluminium；In halogen compound of the copper source selected from copper, nitrate, sulfate, acetate at least
It is a kind of；Silicon source is in organosilicon, amorphous silica, Ludox, solid oxidation silicon, silica gel, diatomite or waterglass
It is at least one；Phosphorus source is at least one of orthophosphoric acid, monoammonium phosphate or diammonium hydrogen phosphate；Inorganic base is alkali metal or alkaline earth
The hydroxide of metal is at least one.
In above-mentioned technical proposal, it is preferred that silicon source is selected from least one of aluminate or meta-aluminate；Silicon source is selected from nothing
At least one of amorphous silicon dioxide, Ludox or solid oxidation silicon；Phosphorus source is at least one in orthophosphoric acid, monoammonium phosphate
Kind；Inorganic base is at least one for LiOH, NaOH or KOH.
In above-mentioned technical proposal, it is preferred that the template being used to prepare needed for Cu-SSZ-13 molecular sieves is mantoquita, chelating
Agent and/or copper amine chelate, wherein chelating agent select mixture to be selected from ethylenediamine, diethylenetriamine, triethylene tetramine, four ethene five
At least one of amine, 1,10- Phens, 2,2- bipyridyls or 4,4- bipyridyls；It is used to prepare needed for SAPO-11 molecular sieves
Organic formwork agent be organic amine, selected from 4-propyl bromide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetraethyl hydrogen-oxygen
Change ammonium, tetrabutylammonium bromide, tetrabutylammonium hydroxide, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine or ethamine
At least one of；Solvent is in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, ethanol, ethylene glycol or deionized water
At least one.
In above-mentioned technical proposal, it is preferred that chelating agent is in diethylenetriamine, triethylene tetramine, tetraethylenepentamine
At least one, solvent are at least one of n,N-Dimethylformamide, ethanol or deionized water；
To solve the three of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Cu-SSZ-13/SAPO-11 is compound
Structure molecular screen is as catalyst, for the reaction of methanol hydro carbons, in hydrogenation reaction and olefin cracking reaction.
In above-mentioned technical proposal, the application method of Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst is as follows：On
Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst is stated in unsaturated compound or high molecular with unsaturated bond
Application in hydrogenation；It is furthermore preferred that catalyst suitable for cracking carbon nine and its above hydrocarbon-fraction unsaturated component plus
Hydrogen process.
In above-mentioned technical proposal, the application method of Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst is as follows：On
State application of the Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst in hydrocarbon cracking reaction；Preferably, cracking reaction
Reaction condition is：500~650 DEG C of reaction temperature, diluent/raw material weight is than 0~1: 1,1~30h of liquid phase air speed-1, reaction pressure
Power -0.05~0.2MPa.Hydro carbons is preferably comprising at least one alkene, more preferably includes at least one C4And above alkene.
In above-mentioned technical proposal, the application method of Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst is as follows：On
State, application of the Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst in methanol hydrocarbon reaction；Preferably, methanol
The reaction condition that conversion prepares hydro carbons is：Be 400~600 DEG C in reaction temperature using methanol as raw material, reaction pressure for 0.01~
10MPa, methanol weight air speed are 0.1~15h-1。
The content of metallic element Cu is divided in plasma P erkin-Elmer 3300DV ICP in composite molecular sieves
It is measured in analyzer, concrete operation method is as follows：
Sample is placed in 100 DEG C of oven for drying 2h, weighs 0.2~0.5g of sample after drying afterwards in platinum crucible or plastics
In king's crucible, it is 1 to add 10 drop volume ratios：With 8mL hydrofluoric acid, heating, often shakes and accelerates sample to decompose, treat 1 sulfuric acid solution
In crucible solution it is clear it is thorough after, solution is steamed to white cigarette and is emitted to the greatest extent, removes cooling, adds volume ratio for 1:1 hydrochloric acid 5mL and suitable quantity of water.Add
Heat of solution residue, then moves into 100mL volumetric flasks, and crucible is eluted with water and dilute to scale and shakes up, the solution that will have been configured
ICP spectrometer analysis are introduced, record percentage composition.
Composite molecular sieves provided by the invention have the pore passage structure feature and acidic character of two kinds of molecular sieves, and body concurrently
Reveal and carry out good cooperative effect.Change the two-phase proportion in composite molecular screen by optimising and adjustment synthesis condition in situ to be had
There are optimal pore passage structure and suitable acid composite molecular sieves, the reaction process of hydrocarbon processed is converted for methanol, is being set
In the range of fixed appreciation condition, methanol conversion 100%, the once through yield of ethene, propylene and isobutene reaches as high as
75.9%, while catalyst is with good stability, achieves preferable technique effect.
The present invention is further elaborated below by embodiment.
Embodiment
【Embodiment 1】
The synthesis of Cu-SSZ-13/SAPO-11 composite molecular sieves
Weigh the aluminum nitrate [Al (NO of 4121.21g3)3·9H2O, purity >=98%wt., 10.98mol] it is molten
In 37366.52mL deionized waters, the solution is divided into two parts respectively 60% and 40% by mass fraction after stirring evenly, is remembered
For solution S1And solution S2, by the Ludox [SiO of 22101.36g2, 40%wt, 147.34mol], the copper acetate of 2166.88g
[Cu(OAc)2·H2O, purity >=98%wt., 10.83mol] and 2050.12g tetraethylenepentamine [TEPA, 10.83mol]
Put into S1It is after being sufficiently stirred that the above-mentioned solution adjusting of sodium hydroxide [NaOH, the 55.01mol] addition of 2200.22g is molten in solution
Liquid pH value continues to obtain solution S after stirring 5h between 9~101’；By the phosphoric acid [H of 2012.79g3PO4, 85%wt.,
17.46mol], the acidic silicasol [SiO of 2077.05g2, 40wt%, 13.85mol] and 208.03g triethylamine [DEA,
2.06mol] input S2In solution, stirring 1h obtains solution S2’；By solution S1' and solution S2' it is respectively placed in hydro-thermal process at 90 DEG C
18h, afterwards by solution S1' and solution S2' uniformly mix, closed stirring 10h at 120 DEG C；By above-mentioned stirring mixture, then it is placed in
145 DEG C of crystallization 15d, product is filtered, 110 DEG C of dry 5h after washing, then heats to 400 DEG C, constant temperature calcining 12h must both be produced
Thing, is denoted as CZP-1.The reactant stoichiometric ratio of the system is as follows：Al：Si：P：T：S：OH=1: 14.68: 1.62: 1.17:
263.99: 5.01, show that Cu/SSZ-13 molecular sieve contents are 61.2% in CZP-1 molecular sieves through ICP tests and XRD analysis,
SAPO-11 contents are 38.8%.
【Embodiment 2】
The synthesis of Cu-SSZ-13/SAPO-11 composite molecular sieves
Weigh the aluminum nitrate [Al (NO of 3.75g3)3·9H2O, purity >=98%wt., 0.01mol] molten 111.55mL go from
In sub- water, the solution is divided into two parts respectively 50% and 50% by mass fraction after stirring evenly, is denoted as solution S1And solution
S2, by the white carbon [SiO of 1.21g2, 99wt.%, 0.02mol], the copper sulphate [CuSO of 4.82g4·5H2O, 0.02mol] with
And ethylenediamine [DEA, 0.06mol] the input S of 3.61g1In solution, after being sufficiently stirred by the sodium hydroxide of 39.99g [NaOH,
1.0mol] above-mentioned solution adjusting solution ph is added between 11~12, continue to obtain solution S after stirring 2.5h1’；By 10.55g
Ammonium dihydrogen phosphate [NH4H2PO4, 0.10mol], the white carbon [SiO of 0.61g2, 99wt.%, 0.01mol] and 18.35g
Ethylenediamine [EDA, 0.30] puts into S2In solution, stirring 0.5h obtains solution S2’；By solution S1' and solution S2' it is respectively placed in 80 DEG C
Lower hydro-thermal process 24h, afterwards by solution S1' and solution S2' uniformly mixing, 120 DEG C of closed stirring 24h；It is stirred above-mentioned
Thing, then 200 DEG C of crystallization 5h are placed in, product is filtered, 80 DEG C of dry 8h after washing, then heats to 550 DEG C, constant temperature calcining 9h was both
Product is obtained, is denoted as CZP-2.The reactant stoichiometric ratio of the system is as follows：Al：Si：P：T：S：OH=1: 3: 10: 32: 10:
6175, show that Cu/SSZ-13 molecular sieve contents are 52.6%, SAPO-11 in CZP-2 molecular sieves through ICP tests and XRD analysis
Content is 47.4%.
【Embodiment 3】
The synthesis of Cu-SSZ-13/SAPO-11 composite molecular sieves
Claim the aluminum sulfate [Al of 2110.55g2(SO4)3·18H2O, purity >=98wt.%, 3.17mol] it is dissolved in
In 16322.09mL deionized waters, the solution is divided into two parts respectively 40% and 60% by mass fraction after stirring evenly, is remembered
For solution S1And solution S2, by the acidic silicasol [SiO of 997.31g2, 40wt.%, 6.65mol], 1024.35g Cu-TETA
Chelate [is made, 4.97mol, n (Cu by mantoquita and triethylene tetramine：TETA=1:1) S] is put into1In solution, after being sufficiently stirred
By the potassium hydroxide [Ca (OH) of 2506.56g2, 44.68mol] and above-mentioned solution adjusting solution ph is added between 10~11, after
Solution S is obtained after continuous stirring 5h1’；By the phosphoric acid [H of 166.64g3PO4, 85%wt., 1.44mol], the acid silicon of 1010.18g it is molten
Glue [SiO2, 40wt.%, 6.73mol] and 2211.38g tetrabutylammonium bromide [TPABr, 8.31mol] input S2In solution,
Stirring 1.5h obtains solution S2’；By solution S1' and solution S2' hydro-thermal process 0.5h at 120 DEG C is respectively placed in, afterwards by solution S1’
With solution S2' uniformly mixing, 120 DEG C of closed stirring 0.5h；By above-mentioned stirring mixture, then 165 DEG C of crystallization 7d are placed in, product warp
80 DEG C of dry 9h after filtering, washing, then heat to 650 DEG C, constant temperature calcining 9h both obtains product, is denoted as CZP-3.The system it is anti-
Answer thing stoichiometry ratio as follows：Al：Si：P：T：S：OH=1: 4.20: 0.45: 1.19: 307.60: 14.09, through ICP test with
And XRD analysis show that Cu/SSZ-13 molecular sieve contents are that 41.3%, SAPO-11 contents are 58.7% in CZP-3 molecular sieves.
【Embodiment 4】
The synthesis of Cu-SSZ-13/SAPO-11 composite molecular sieves
Weigh the aluminum sulfate [Al of 10985.11g2(SO4)3·18H2O, purity >=98wt.%, 16.50mol] it is dissolved in
In 35127.55mL deionized waters, the solution is divided into two parts respectively 80% and 20% by mass fraction after stirring evenly, is remembered
For solution S1And solution S2, by the white carbon [SiO of 9211.36g2, 99wt.%, 153.52mol], the Cu-TEPA of 7194.22g
[28.15mol, n (Cu is made by mantoquita and tetraethylenepentamine in chelate：TEPA=1:1) S] is put into1In solution, after being sufficiently stirred
The lithium hydroxide [LiOH, 925.49mol] of 22111.66g is added into above-mentioned solution and adjusts solution ph between 11~12, after
Solution S is obtained after continuous stirring 1.5h1’；By the phosphoric acid [H of 15332.96g3PO4, 85%wt., 132.99mol], 10788.64g it is white
Carbon black [SiO2, 99wt.%, 179.81mol] and 8868.68g ethamine [EA, 193.64mol] input S2In solution, stirring
12h obtains solution S2’；By solution S1' and solution S2' hydro-thermal process 6h at 105 DEG C is respectively placed in, afterwards by solution S1' and solution S2’
Uniformly mixing, 120 DEG C of closed stirring 3h；By above-mentioned stirring mixture, then 185 DEG C of crystallization 3d are placed in, product is filtered, after washing
110 DEG C of dry 9h, then heat to 650 DEG C, and constant temperature calcining 10h both obtains product, is denoted as CZP-4, the reactant chemistry of the system
It is as follows to measure ratio：Al：Si：P：T：S：OH=1: 20.20: 8.06: 13.46: 118.27: 56.09, divide through ICP tests and XRD
Analysis shows that Cu/SSZ-13 molecular sieve contents are that 82.1%, SAPO-11 contents are 17.9% in CZP-3 molecular sieves.
【Embodiment 5】
The synthesis of Cu-SSZ-13/SAPO-11 composite molecular sieves
Weigh the sodium aluminate [NaAlO of 15.75g2, purity >=98%wt., 0.19mol] it is dissolved in 211.98mL deionized waters
In, the solution is divided into two parts respectively 21% and 79% by mass fraction after stirring evenly, is denoted as solution S1And solution S2, will
White carbon [the SiO of 60.12g2, 99%wt., 1.0mol], the copper nitrate [Cu (NO of 118.14g3)2·3H2O, 99%wt.,
0.50mol] and 94.65g tetraethylenepentamine [TEPA, 0.50mol] input S1In solution, by the hydrogen of 39.92g after being sufficiently stirred
Sodium oxide molybdena [NaOH, 0.99mol] adds above-mentioned solution and adjusts solution ph between 8~9, continues to obtain solution after stirring 2.5h
S1’；By the diammonium hydrogen phosphate [(NH of 131.98g4)2HPO4, 0.99mol], the white carbon [SiO of 12.12g2, 99%wt.,
0.20mol] and 101.16g di-n-propylamine [DPA, 0.99mol] input S2In solution, stirring 12h obtains solution S2’；By solution
S1' and solution S2' hydro-thermal process 9h at 105 DEG C is respectively placed in, afterwards by solution S1' and solution S2' uniformly mixing, 120 DEG C are closed
Stir 3h；By above-mentioned stirring mixture, then 170 DEG C of crystallization 6d are placed in, product is filtered, 120 DEG C of dry 6h, Ran Housheng after washing
For temperature to 550 DEG C, constant temperature calcining 8h both obtains product, is denoted as CZP-5.The reactant stoichiometric ratio of the system is as follows：Al：Si：P：
T：S：OH=1: 6.23: 5.21: 7.84: 62: 5.21, show Cu/SSZ- in CZP-5 molecular sieves through ICP tests and XRD analysis
13 molecular sieve contents are that 23.6%, SAPO-11 contents are 76.4%.
【Embodiment 6~20】
According to the method for embodiment 5, raw materials used as shown in table 1, control reaction sorting different ratio (table 2), is closed respectively
Into Cu-SSZ-13/SAPO-11 composite molecular sieves are gone out, the ratio of Cu-SSZ-13 and SAPO-11 is shown in Table 3 in material.
Table 1
Table 2
【Embodiment 21】
Application of the Cu-SSZ-13/SAPO-11 composite molecular sieves in methanol converts hydrocarbon reaction processed
The CZP-3 molecular sieves that Example 3 synthesizes, carry out ammonium at 85 DEG C with 4.5wt% ammonium nitrate solutions and exchange 2.5h.Production
Thing is filtered, washing, at 110 DEG C after dry 5h, repeats ammonium of progress and exchanges, filtered, washing, dry 5h at 110 DEG C
Afterwards, roast 4h at 550 DEG C, Hydrogen composite molecular sieves be made, then tabletting, break into pieces, sieve, take the particle of 12~20 mesh
It is spare.Using methanol as raw material, with a diameter of 15 millimeters of fixed bed reactors, in 490 DEG C, mass space velocity 1.5h-1, pressure be
Checked and rated under conditions of 0.55MPa, ethene, propylene and isobutene yield reach 75.9%, achieve preferable technique effect.
Table 3
| Sample number into spectrum | Cu-SSZ-13 contents (%) | SAPO-11 contents (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 |
【Embodiment 22】
Application of the Cu-SSZ-13/SAPO-11 composite molecular sieves in methanol converts hydrocarbon reaction processed.
The CZP-4 molecular sieves that Example 4 synthesizes, catalyst is made using the method for preparing catalyst of embodiment 21, with
Methanol is raw material, with a diameter of 15 millimeters of fixed bed reactors, in 400 DEG C, mass space velocity 0.1h-1, pressure be 0.01MPa
Under the conditions of check and rate, ethene, propylene and isobutene yield reach 59.1%, achieve preferable technique effect.
【Embodiment 23】
Application of the Cu-SSZ-13/SAPO-11 composite molecular sieves in methanol converts hydrocarbon reaction processed
The CZP-6 molecular sieves that Example 6 synthesizes, catalyst is made using the method for preparing catalyst of embodiment 21, with
Methanol is raw material, with a diameter of 15 millimeters of fixed bed reactors, in 460 DEG C, mass space velocity 15h-1, pressure be 10MPa bar
Checked and rated under part, ethene, propylene and isobutene yield reach 62.1%, achieve preferable technique effect.
【Embodiment 24】
Application of the Cu-SSZ-13/SAPO-11 composite molecular sieves in methanol converts hydrocarbon reaction processed
The CZP-16 molecular sieves that Example 16 synthesizes, catalyst is made using the method for preparing catalyst of embodiment 21,
Using methanol as raw material, with a diameter of 15 millimeters of fixed bed reactors, in 530 DEG C, mass space velocity 7.5h-1, pressure 4.9MPa
Under conditions of check and rate, ethene, propylene and isobutene yield reach 70.2%, achieve preferable technique effect.
【Embodiment 25】
Application of the Cu-SSZ-13/SAPO-11 composite molecular sieves in methanol converts hydrocarbon reaction processed
The CZP-19 molecular sieves that Example 19 synthesizes, catalyst is made using the method for preparing catalyst of embodiment 21,
Using methanol as raw material, with a diameter of 15 millimeters of fixed bed reactors, in 600 DEG C, mass space velocity 2.6h-1, pressure 1.9MPa
Under conditions of check and rate, ethene, propylene and isobutene yield reach 68.9%, achieve preferable technique effect.
【Embodiment 26】
Applications of the mechanical mixture Cu-SSZ-13 with SAPO-11 molecular sieves in methanol converts hydrocarbon reaction processed
SAPO-11 molecular sieves processed and self-control Cu-SSZ-13 molecular sieves are derived from, according to two kinds of molecular sieve ratios of embodiment 8
The mechanical mixture of progress, is checked and rated in the way of embodiment 21, and ethene, propylene and isobutene yield reach 56.9%.
【Embodiment 27】
Applications of the mechanical mixture Cu-SSZ-13 with SAPO-11 molecular sieves in methanol converts hydrocarbon reaction processed
SAPO-11 molecular sieves processed and self-control Cu-SSZ-13 molecular sieves are derived from, according to two kinds of molecular sieve ratios of embodiment 11
The mechanical mixture of progress, is checked and rated in the way of embodiment 21, and ethene, propylene and isobutene yield reach 57.1%.
【Embodiment 28】
SAPO-11 molecular sieves processed and self-control Cu-SSZ-13 molecular sieves are derived from, according to two kinds of molecular sieve ratios of embodiment 5
The mechanical mixture of progress, is checked and rated in the way of embodiment 21, and ethene, propylene and isobutene yield reach 52.6%.
【Comparative example 1】
SAPO-11 molecular sieves processed are derived from, catalyst are made using the method for preparing catalyst of embodiment 21, according to embodiment
23 mode is checked and rated, and ethene, propylene and isobutene yield reach yield up to 15.1%.
【Comparative example 2】
Cu-SSZ-13 molecular sieves processed are derived from, catalyst are made using the method for preparing catalyst of embodiment 21, according to implementation
The mode of example 23 is checked and rated, and ethene, propylene and isobutene yield reach 40.7%.
【Comparative example 3】
SSZ-13 molecular sieves processed are derived from, catalyst are made using the method for preparing catalyst of embodiment 21, according to embodiment
23 mode is checked and rated, and ethene, propylene and isobutene yield reach 31.3%.
【Embodiment 29】
Application of the Cu-SSZ-13/SAPO-11 composite molecular sieves in hydrogenation reaction
The CZP-14 molecular sieves that Example 14 synthesizes, catalyst is made using the method for preparing catalyst of embodiment 21,
By catalyst in 1.3L/min flow of pure hydrogen, 15h is reduced at 480 DEG C, obtains metal mold Cu-SSZ-13/SAPO-11 molecules
Sieve.Since aromatic hydrocarbons accounts for 65~80% in cracking carbon nine and its above hydrocarbon-fraction, contain a large amount of polymerizable unsaturated components at the same time,
This test example selects cracking carbon nine and its above hydrocarbon, and (specific component is shown in Table obtained raw material according to a certain ratio with saturated hydrogenation oil
4) catalyst hydrogenation activity test of the present invention, is carried out.Process conditions are：72 DEG C, pressure 2.2MPa of inlet temperature, green oil air speed
LHSV=2.1h-1, hydrogen to oil volume ratio H2/ feedstock oil=509：1, experimental result is shown in Table 4.
Table 4
【Comparative example 4】
Take Cu/Al2O3-SiO2Catalyst, carries out hydrogenation activity test, as a result such as table 5 according to the condition of embodiment 26.
Table 5
【Embodiment 27】
Application of the Cu-SSZ-13/SAPO-11 composite molecular sieves in olefin cracking reaction
The CZP-20 molecular sieves that embodiment 20 synthesizes are chosen, catalysis is made using the method for preparing catalyst of embodiment 21
Agent, reaction temperature be 660 DEG C, reaction pressure 0.03MPa, weight space velocity 1.5h-1Under conditions of check and rate, the results are shown in Table 6.
【Comparative example 5】
Take SiO2/Al2O3Molar ratio is 11 modenite, and catalysis is made using the method for preparing catalyst of embodiment 21
Agent, is checked and rated in the way of embodiment 27, as a result such as table 6.
【Comparative example 6】
Take SiO2/Al2O3Molar ratio is 35 β zeolites, and catalyst is made using the method for preparing catalyst of embodiment 21,
Checked and rated in the way of embodiment 27, as a result such as table 6.
【Comparative example 7】
Take SiO2/Al2O3Molar ratio is 12 Y zeolites, and catalyst is made using the method for preparing catalyst of embodiment 21,
Checked and rated in the way of embodiment 27, as a result such as table 6.
【Comparative example 8】
Take SiO2/Al2O3Molar ratio is 51 ZSM-5 molecular sieve, is made and urged using the method for preparing catalyst of embodiment 21
Agent, is checked and rated in the way of embodiment 27, as a result such as table 6.
Table 6
Claims (10)
1. a kind of Cu-SSZ-13/SAPO-11 composite molecular sieves, it is characterised in that the Cu-SSZ-13/SAPO-11 is answered
Closing structure molecular screen has two kinds of thing phases of Cu-SSZ-13 and SAPO-11, the wherein weight percentage of Cu-SSZ-13 molecular sieves
For 1~99%；The weight percentage of SAPO-11 molecular sieves is 1~99%, its XRD diffracting spectrum is 8.09 ± 0.05 in 2 θ,
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 there is diffraction maximum at ± 0.1,43.13 ± 0.1.
2. Cu-SSZ-13/SAPO-11 composite molecular sieves according to claim 1, it is characterised in that with Cu-SSZ-13/
The weight of SAPO-11 composite molecular sieves, Cu-SSZ-13 molecular sieves in the composite molecular sieves
Weight percentage is 5~95%；The weight percentage of SAPO-11 molecular sieves is 5~95%.
3. Cu-SSZ-13/SAPO-11 composite molecular sieves according to claim 1, it is characterised in that with Cu-SSZ-13/
The weight of SAPO-11 composite molecular sieves, Cu-SSZ-13 molecular sieves in the composite molecular sieves
Weight percentage is 30~75%；The weight percentage of SAPO-11 molecular sieves is 25~70%.
4. the Cu-SSZ-13/SAPO-11 composite molecular sieves described in claim 1, using raw materials used molar ratio as：n
(Si/Al)=1~∞, n (P/Al)=0.01~1000, n (template T/Al)=1~5000, n (solvent S/Al)=10~
10000, n (OH/Al)=1~1000, its synthetic method include the following steps：
A, silicon source and solvent are mixed to form solution S first, then solution is divided into two parts and is denoted as solution S1And solution S2；
B, a part of silicon source, mantoquita, chelating agent and/or copper amine chelate are added into S10.5~5h is sufficiently stirred in middle solution, and
Inorganic base regulation system pH value is added in whipping process solution S is obtained between 8~121’；
C, organic formwork agent needed for remaining silicon source, phosphorus source and synthesis SAPO-11 molecular sieves is added into S2In solution, stirring 0.5
~5h, obtains solution S2’；
D, by solution S1' and solution S2' pre- 0.5~5h of Crystallizing treatment at 80~120 DEG C is respectively placed in, afterwards by solution S1' with it is molten
Liquid S2' uniformly mix, 1~10h of closed stirring at 80~120 DEG C, forms uniform crystallization mixture；
E, the crystallization mixture of above-mentioned steps d being placed in 100~200 DEG C, 5~168h of crystallization, product is filtered, 80 after washing~
120 DEG C of dryings, then heat to 400~650 DEG C, 4~12h of constant temperature calcining.
5. the synthetic method of composite molecular sieves according to claim 4, it is characterised in that raw materials used molar ratio
For：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 S2Weight ratio be 0.1~10:1；Institute in step b
Total silicon source mass percent is accounted for as 5~95% with silicon source.
6. the synthetic method of Cu-SSZ-13/SAPO-11 composite molecular sieves according to claim 4, it is characterised in that use
The molar ratio of raw material is：N (Si/Al)=1~200, n (P/Al)=0.5~50, n (template T/Al)=20~200, n
(solvent S/Al)=200~600, n (OH/Al)=3~50；Solution S in step a1And solution S2Weight ratio be 0.2~5:1；
Silicon source used accounts for total silicon source mass percent as 15~85% in step b.
7. the synthetic method of composite molecular sieves according to claim 4, silicon source is selected from aluminate, meta-aluminate, aluminium
At least one of hydroxide, the oxide of aluminium or mineral containing aluminium；Copper source is selected from halogen compound, nitrate, the sulphur of copper
At least one of hydrochlorate, acetate；Silicon source be selected from organosilicon, amorphous silica, Ludox, solid oxidation silicon, silica gel,
At least one of diatomite or waterglass；Phosphorus source is at least one of orthophosphoric acid, monoammonium phosphate or diammonium hydrogen phosphate；Nothing
Machine alkali is at least one for the hydroxide of alkali or alkaline earth metal.
8. the synthetic method of composite molecular sieves according to claim 4, it is characterised in that be used to prepare Cu-SSZ-13 points
Template needed for son sieve is mantoquita, chelating agent and/or copper amine chelate, and wherein chelating agent selects mixture to be selected from ethylenediamine, diethyl
At least one in alkene triamine, triethylene tetramine, tetraethylenepentamine, 1,10- Phens, 2,2- bipyridyls or 4,4- bipyridyls
Kind；It is organic amine to be used to prepare the organic formwork agent needed for SAPO-11 molecular sieves, selected from 4-propyl bromide, tetrapropyl hydrogen-oxygen
Change ammonium, tetraethylammonium bromide, tetraethyl ammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, triethylamine, n-butylamine, two
At least one of n-propylamine, diisopropylamine, ethylenediamine or ethamine；Solvent is N,N-dimethylformamide, N, N- dimethyl second
At least one of acid amides, ethanol, ethylene glycol or deionized water.
9. the synthetic method of Cu-SSZ-13/SAPO-11 composite molecular sieves according to claim 4, it is characterised in that aluminium
Source is selected from least one of aluminate or meta-aluminate；Silicon source is selected from amorphous silica, Ludox or solid oxidation silicon
At least one of；Phosphorus source is at least one of orthophosphoric acid, monoammonium phosphate；Inorganic base is LiOH, NaOH or KOH at least one
Kind；Chelating agent is selected from least one of diethylenetriamine, triethylene tetramine, tetraethylenepentamine；Solvent is N, N- dimethyl methyls
At least one of acid amides, ethanol or deionized water.
10. any Cu-SSZ-13/SAPO-11 composite molecular sieves described in claims 1 to 3 are used for as catalyst
In the reaction of methanol hydro carbons, hydrogenation reaction and olefin cracking reaction.
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