CN116078425A - 一种金属杂化共生分子筛及其水热合成方法 - Google Patents
一种金属杂化共生分子筛及其水热合成方法 Download PDFInfo
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- CN116078425A CN116078425A CN202211669797.5A CN202211669797A CN116078425A CN 116078425 A CN116078425 A CN 116078425A CN 202211669797 A CN202211669797 A CN 202211669797A CN 116078425 A CN116078425 A CN 116078425A
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- metal
- molecular sieve
- hybridization
- symbiotic
- hydrothermal synthesis
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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 218
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 211
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 152
- 239000002184 metal Substances 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 71
- 238000009396 hybridization Methods 0.000 title claims abstract description 41
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 238000002425 crystallisation Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 238000001640 fractional crystallisation Methods 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 238000006900 dealkylation reaction Methods 0.000 abstract description 6
- 238000007323 disproportionation reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000020335 dealkylation Effects 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006317 isomerization reaction Methods 0.000 abstract description 3
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 15
- 239000002131 composite material Substances 0.000 description 15
- 229910052680 mordenite Inorganic materials 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 8
- 238000001237 Raman spectrum Methods 0.000 description 8
- 230000004075 alteration Effects 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline earth Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000705164 Gelis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 208000012839 conversion disease Diseases 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940095060 magnesium tartrate Drugs 0.000 description 1
- MUZDLCBWNVUYIR-ZVGUSBNCSA-L magnesium;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Mg+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O MUZDLCBWNVUYIR-ZVGUSBNCSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003738 xylenes Chemical class 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
本发明涉及一种金属杂化共生分子筛及其水热合成方法。该金属杂化共生分子筛由含有至少一种金属和二种微孔分子筛形成的共生分子筛所构成,其中金属以团簇或单原子状态位于共生分子筛晶粒内部和表面,并以金属、金属氧化物和/或离子状态存在。该金属杂化共生分子筛制备是采用在共生分子筛水热合成凝胶中掺入金属前驱体化合物,通过分步晶化手段而直接形成金属与共生分子筛结合的整体晶体结构的方式合成制得。本发明中所提供一种特殊组成结构的金属杂化共生分子筛、及其高效水热合成方法,该金属杂化分子筛具有孔道限域分散金属高活性与共生分子筛特殊的强酸性质,在芳烃歧化、芳烃脱烷基、加氢裂化和烃类异构化等反应催化上具有重要的应用价值。
Description
技术领域
本发明涉及一种金属杂化共生分子筛及其水热合成方法,属于沸石分子筛材料及其合成技术领域。
背景技术
沸石分子筛因其较高的催化活性、良好的择形性能和较好的催化稳定性,被广泛地应用于石油加工等领域。然而,催化反应过程对催化剂的催化反应活性和稳定性具有诸多的要求,往往需要借助金属完成催化剂的改性。目前,金属对催化剂的改性,主要采用浸渍法和离子交换法实现分子筛中引入金属,但是通过离子交换法引入沸石分子筛晶体的金属阳离子数量有限,并且金属阳离子前驱体往往具有较大的尺寸,而难以进入分子筛的孔道。同时采用浸渍法在分子筛中引入金属,容易出现金属/金属物种在分子筛表面聚集形成较大颗粒,难以分散的现象,这在较大程度上限制了金属/分子筛催化剂的性能。
采用原位合成引入金属的方法是解决上述浸渍法和离子交换法在分子筛中引入金属方面性能不足的有效方法,金属在分子筛晶化形成过程中同时被直接引入,使金属嵌入分子筛晶体中,实现了金属/金属物种在分子筛中均匀分散,并且可以防止金属/分子筛材料在使用过程中金属表面聚集导致的性能下降。
中国专利CN105413742A公开了一种沸石包覆贵金属粒子的合成方法,其将含有铂的可溶盐和/或钯的可溶盐的金属盐溶液,与硅源和/或铝源、模板剂、H值调节剂、水混合,经搅拌获得凝胶,并经过烘干得到干胶:然后采用干胶水蒸汽辅助法晶化,并将晶化所得产物在空气气氛下焙烧5-8小时,再在氢气气氛中还原2-4小时。该方法借鉴了蒸汽辅助转化法合成Silicate-1包覆贵金属的特点,在丝光沸石和Beta沸石合成过程中引入成功实现了孔道内含贵金属的沸石分子筛的合成,进而提高了催化剂在轻质烷烃异构化反应中的催化性能。该方法尽管实现了铂/钯等贵金属的在丝光沸石Beta沸石中的高分散度,但此方法过程复杂,操作不易控制,重现性差,能耗较高,规模化实施的难度较大,难于实现工业化生产应用。
中国专利CN113649064A公开了一种沸石分子筛负载金属催化剂及其合成方法,该方法采用两步晶化法,先使硅铝凝胶在低温预晶化,再加入金属盐溶液进行高温晶化。该方法解决了现有原位包覆法存在的由于金属盐溶液的掺入增加了晶体的生长难度的问题,同时也避免了二次调节体系pH或额外添加晶种的步骤,简化了工艺流程,提高了生产效率并降低成本。然而,该方法中采用高温晶化阶段加入金属盐溶液快速水解沉淀与聚集,使金属在沸石分子筛中分散不理想,且金属主要为用于加氢反应的过渡金属或贵金属,也不适用于在分子筛金属改性中常用碱土、稀土等金属的酸性调节。
由于每一种沸石分子筛材料制备的固体酸催化剂酸性质,受该分子筛材料本身酸性质(强度/数量)的限制。人们研究发现当二种不同沸石分子筛在合成过程中以共生的方式形成一定比例的共生分子筛孪晶复合(具有二种分子筛晶相复合)时,其共生分子筛材料的酸性质(强度/数量)会高于相同比例的二种不同沸石分子筛以简单机械混合方式的形成共混分子筛,并且在其孔结构上也有所差异。所以采用共生分子筛材料可以制备出更强酸性的固体酸催化剂,从而获得更优的催化剂反应性能。这种特殊酸性质被认为来自于特殊的复合分子筛中的特别结构二种晶相交界处;但是,目前对于共生分子筛合成过程、尤其是共生分子筛孪晶中二种分子筛晶相比例的控制难度很大,且合成操作的重复性较低。
CN102909061A公开了一种 EU-1/ZSM-5 复合分子筛,该复合分子筛同时具有 EU-1 分子筛晶相和 ZSM-5 分子筛晶相,ZSM-5 分子筛镶嵌在 EU-1 分子筛周围,由此制成的催化剂被应用于以甲苯和/或C9芳烃为原料制取苯和二甲苯反应过程。在EU-1/ZSM-5复合分子筛水热合成方法中的凝胶物料配制是将 EU-1 分子筛、硅源、水和模板剂按配比充分混合均匀,其晶化过程是新形成的ZSM-5 分子筛晶相生长在原有的EU-1 分子筛晶相表面上,造成在该EU-1/ZSM-5 复合分子筛中EU-1与ZSM-5 二种分子筛晶相分散度低,使复合分子筛的晶相交界面较少,且需要大量的EU-1分子筛作为晶种。
CN102909063A以相似的方法合成了一种EU-1/Beta复合分子筛,该EU-1/Beta复合分子筛的结构为 Beta 分子筛晶相紧密包裹在EU-1分子筛的周围。将EU-1分子筛、硅源、铝源、碱、水和模板剂按配比混合均匀得到物凝胶装入晶化釜中升温至 140℃-150℃,水热晶化3-5天制得EU-1/Beta复合分子筛。
通过方法优化改进,CN102874839 A提供了一种核壳结构ZSM-5/丝光沸石复合分子筛的合成方法,ZSM-5 分子筛位于晶体的核心,丝光沸石为壳层,紧紧包裹在 ZSM-5 分子筛的外层。首先在密闭条件下对丝光沸石进行碱处理,按照一定摩尔配比将无机碱、铝源、硅源和水搅拌混合,然后加入结构导向剂(丝光沸石模板剂)、ZSM-5 沸石和氯化物,在160-180℃温度下晶化15-45小时得到产品。CN101722034A也公开了一种丝光沸石/ZSM-5核壳型分子筛材料的制备方法,主要解决以往技术中存在的丝光沸石和ZSM-5 沸石分子筛不易复合生长的问题。本发明的要点是将丝光沸石晶粒在改性剂溶液中进行处理,再改性剂处理后丝光沸石晶粒投入ZSM-5合成体系混合均匀水热晶化,制得丝光沸石/ZSM-5复合分子筛。CN102838128A发明了一种丝光沸石/ZSM-5共生分子筛的制备方法,采用两步晶化,将无机碱、铝源、硅源充分混合后加入丝光沸石晶种,经老化,晶化,再加硅源,再次晶化,所得产物经过分离、洗涤、干燥,得到丝光沸石/ZSM-5 共生分子筛。本方法虽可减少丝光沸石模板剂用量,但需二次晶化、分开加入硅源,且合成操作复杂、时间长、难度大,重复性不易控制。
本发明专利技术方案是将金属杂化分子筛与复合晶相共生分子筛的优点相结合,通过研究试验解决金属杂化分子筛合成中多种金属在沸石分子筛中分散问题、复合共生分子筛合成中分子筛晶相比例的控制与合成重复性低的困难、以及金属杂化和复合共生合成条件的匹配结合,提供一种高效金属杂化共生分子筛及其水热合成方法,通过在分子筛合成中直接掺入少量金属并与共生分子筛结合而形成整体分子筛晶体结构,该金属杂化共生分子筛具有孔道限域高分散金属活性与共生分子筛酸性质,在芳烃歧化、芳烃脱烷基、加氢裂化和烃类异构化等反应催化上具有重要的应用价值。
发明内容
本发明主要解决的技术问题是传统分子筛在金属改性过程中金属分布不均匀,容易在分子筛表面上金属/金属物种聚集形成较大颗粒、难以分散的问题。同时解决金属杂化分子筛合成过程中,金属在制得的分子筛产品中团聚严重、分布不均,且金属盐溶液的引入导致分子筛结晶度较低,而较大程度地限制了金属-分子筛催化剂性能的难题,以及复合共生分子筛合成中分子筛晶相比例的控制与合成重复性低的困难、以及金属杂化和复合共生合成条件难以匹配结合的难题。本发明专利采用在共生分子筛水热合成凝胶中掺入金属前驱体化合物,并通过分步晶化手段,而直接形成金属与共生分子筛结合的整体晶体结构的技术方案,合成并获得了特殊组成结构的金属杂化共生分子筛,可用于高性能的双功能反应催化剂制备。
为解决上述技术问题,本发明所采用的技术方案如下:
一种金属杂化共生分子筛:所述的金属杂化共生分子筛由至少一种金属和两种微孔分子筛形成的共生分子筛所构成。
作为优选,所述的金属杂化共生分子筛中的金属以团簇或单原子状态位于共生分子筛晶粒内部和表面,并以金属、金属氧化物和/或离子状态存在。
作为优选,所述的金属杂化共生分子筛中的金属包含Pd、Pt、Ru、Ni、Cu、Au、Mo、Co、La、Ce、Zr、Sn、Ti、W、Cr、V、Zn、Mg、Ca、Bi、Re中的一种或多种。其中金属优选自Pd、Pt、Ni、Mo、Co、La、Ce、Sn、Ti、W、Zn、Re中的一种或多种。
作为优选,其中金属所占金属杂化共生分子筛的质量分数为0.01%~10.0%。
作为优选,所含的共生分子筛构成为ZSM-12、ZSM-5、MOR、MCM-56、Beta、MCM-22、Y分子筛中的至少二种或几种。
作为优选,所述金属杂化共生分子筛中所含的共生分子筛的硅铝比为5~200。其中共生分子筛的硅铝比优选为15~100。
一种金属杂化共生分子筛水热合成方法:所述的金属杂化共生分子筛是通过在共生分子筛水热合成凝胶中掺入金属前驱体化合物,使金属直接与共生分子筛结合形成整体晶体结构的方式合成制得。
作为优选,所述的金属前驱体化合物,可以选择是含有金属的胶体溶液、络合物溶液或盐溶液。优选自含有金属的粒径小于3 纳米胶体溶液,或选自含有金属的EDTA、乙酰丙酮、酒石酸等其它不含硫元素的络合物溶液。
作为优选,所述的金属杂化共生分子筛采用分段晶化的方法进行制备。
作为优选,所述的分段晶化的方法,是将硅源、铝源、模板剂、晶种、pH调节剂、水、金属前驱体的化合物溶液混合形成凝胶后,在低温下先完成预晶化处理, 并使金属前驱体化合物均匀分解,然后置于高温下完成晶化过程。晶化所得产物经过过滤、洗涤、焙烧后得到金属杂化共生分子筛成品。
作为优选,所述凝胶具有下列摩尔组成(0.05~10)Na2O:(1.0)Al2O3:(3~220)SiO2:(720~3200)H2O。
作为优选,所述的硅源为硅溶胶、水玻璃、二氧化硅、白炭黑、硅酸钠、正硅酸四乙酯中的一种或几种。
作为优选,所述的铝源为铝酸钠、拟薄水铝石、氢氧化铝、硝酸铝、硫酸铝、异丙醇铝中的一种或几种。
作为优选,所述的模板剂为四丙基氢氧化铵、乙胺、三乙胺、四乙基溴化铵、四乙基氢氧化铵、四丙基溴化铵、正丁胺、六亚甲基亚胺中的一种或几种。
作为优选,所述的pH调节剂为烧碱、纯碱、氨水、盐酸、硝酸、硫酸中的一种或几种。
作为优选,所述的低温阶段温度为50~120℃,晶化4~48 h。
作为优选,所述的高温阶段温度为160~200℃,晶化36~72 h。
作为优选,所述的焙烧温度为500~600℃,在空气气氛下焙烧2~8 h。
作为优选,焙烧后选用铵盐进行交换处理,铵盐可选自醋酸铵、甲酸铵、碳酸铵或草酸铵。
本发明的金属杂化共生分子筛及其合成技术方法是采用在共生分子筛水热合成凝胶中掺入金属前驱体化合物,通过分步晶化手段而直接形成金属与共生分子筛结合的晶体结构整体。具体实施是在硅源、铝源、模板剂、晶种、pH调节剂体系中加入金属前驱体化合物溶液,而组成合成含金属凝胶,先在低温下完成预晶化处理,并使金属前驱体化合物均匀分解,然后置于高温下完成晶化过程,将晶化所得产物经过过滤、洗涤、焙烧后得到金属杂化分子筛。本发明中所提供一种特殊组成结构的金属杂化共生分子筛及其高效可控水热合成方法,该金属杂化分子筛具有孔道限域分散金属高活性与共生分子筛特殊的强酸性质,在芳烃歧化、芳烃脱烷基、加氢裂化和烃类异构化等反应催化上具有重要的应用价值。
具体实施方式
以下结合实施例对本发明进行进一步阐述。
实施例1
将37 g铝酸钠、20.7 g浓硫酸溶解在300 mL去离子水中,完全溶解后制备得到铝源溶液。然后将320.3 g质量分数为27%的水玻璃中充分混合形成硅源溶液与100mL去离子水充分混合形成硅源溶液,然后逐滴滴加到上述的铝源溶液中,完成成胶,然后加入5.2 g四丙基氢氧化铵,然后加入5.8 g 乙酰丙酮铁的水/乙醇溶液,再用乙胺和氨水调节pH至11.15,最终形成的凝胶中的摩尔组成为6 Na2O:Al2O3:35 SiO2:960 H2O。然后加入10.2克ZSM-5晶种,室温搅拌4小时后转移至2 L的高压水热合成釜中,然后升温至120℃,晶化48 h后,然后将反应釜升温至180℃,继续晶化60 h。所得到的晶化产物,经去离子水洗涤、干燥、焙烧后,获得Fe金属-杂化ZSM-5/ZSM-12分子筛;TEM电镜与XRD衍射仪表征分析显示Fe-ZSM-5/ZSM-12分子筛中的ZSM-5/ZSM-12为共生分子筛形态,且ZSM-5/ZSM-12重量比例为79/ 21;化学分析测得其中Fe含量(质量分数)为1.2%,UV-Raman紫外拉曼光谱与STM球差电镜显示Fe以单原子离子和金属氧化物团簇形式的高分散状态存在于杂化分子筛, ICP与XRF的表征结果表明,Fe金属-杂化MOR/ZSM-5分子筛的硅铝比为38。
实施例2
将25 g铝酸钠、25.1克氢氧化钠溶解于2800 g去离子水中,形成铝源溶液,然后加入96 .0g六亚甲基四胺。然后将946.3克质量分数为40%硅溶胶作为硅源,逐滴滴加到上述铝源溶液中,形成凝胶,然后用氨水调节pH至11。最终形成的凝胶中的摩尔组成为7.5Na2O:Al2O3:53 SiO2:1500 H2O。然后加入含有13.1 g钼酸的胶体溶液30 ml,再加入40 gMCM-22晶种,剧烈搅拌以混合均匀,然后室温搅拌4小时后转移至5 L的高压水热合成釜中,然后升温至100℃,晶化24 h后,将反应釜升温至150℃,继续晶化94 h。所得到的晶化产物,经去离子水洗涤、干燥、焙烧后,获得Mo金属-杂化ZSM-5/MCM-22分子筛;TEM透射电镜与XRD衍射仪表征分析显示Mo-ZSM-5/MCM-22分子筛中的ZSM-5/MCM-22为共生分子筛形态,且ZSM-5/MCM-22重量比例为32 / 68;化学分析测得其中Mo含量(质量分数)为3.1%,UV-Raman紫外拉曼光谱与STM球差电镜显示Mo以金属氧化物团簇形式的高分散状态存在于杂化分子筛。ICP与XRF的表征结果表明,W金属-杂化MOR/ZSM-5分子筛的硅铝比为57。
实施例3
将390 克白炭黑在搅拌的状态下逐滴滴加120 mL氨水,形成硅源溶液。然后将198.5克硫酸铝溶解到360.2 g去离子水中,充分溶解后,加入140克氯化钠,充分溶解,形成铝源溶液。然后以450克去离子水作为底料,在剧烈搅拌的条件下,将硅源与铝源均匀混合成胶。加入适量的氨水,将凝胶的pH值调至11.2。最终形成的凝胶中的摩尔组成为8.4Na2O:Al2O3:42 SiO2:861 H2O。完成成胶后,加入62.8 g的硝酸铜与EDTA形成的配合物溶液,然后分别加入10.7克四丙基氢氧化铵和20.4 g Beta晶种,继续搅拌4 h后,转移至5 L的高压水热合成釜中,然后升温至100℃,晶化12 h后,将反应釜升温至170℃,继续晶化48 h。所得到的晶化产物,经去离子水洗涤、干燥、焙烧后,获得的Cu金属-杂化MOR/Beta分子筛;TEM透射电镜与XRD衍射仪表征分析显示Cu-MOR/Beta分子筛中的MOR/Beta为共生分子筛形态,且MOR/Beta重量比例为47 / 53;化学分析测得其中Cu含量(质量分数)为5.1%,UV-Raman紫外拉曼光谱与STM球差电镜显示Cu以单原子离子和团簇金属氧化物形式的高分散状态存在于杂化分子筛,ICP与XRF的表征结果表明,Ni金属-杂化MOR/ZSM-5分子筛的硅铝比为44。
实施例4
将34.5 g 硫酸铝、78.1 g氯化钠溶解在340 mL去离子水中,完全溶解后制备得到铝源溶液。然后将150.3 g质量分数为40%的硅溶胶与100mL去离子水充分混合形成硅源溶液,然后将100.7 g的去离子水与150.2 g的水玻璃作为釜底料,在剧烈搅拌的条件下,向釜底料中同时滴加上述的铝源溶液和硅源溶液,完成成胶,再用乙胺和氨水调节pH至11.35。最终形成的凝胶中的摩尔组成为3.8 Na2O:Al2O3:27 SiO2:1420 H2O。然后加入4.2 g酒石酸镁,并加入10.3克ZSM-5晶种。室温搅拌12小时后转移至2 L的高压水热合成釜中,然后升温至140℃,晶化72 h后,然后将反应釜升温至180℃,继续晶化48 h。所得到的晶化产物,经去离子水洗涤、干燥、520℃焙烧后,获得Mg金属-杂化ZSM-5/MOR分子筛;TEM透射电镜与XRD衍射仪表征分析显示Mg-ZSM-5/MOR分子筛中的ZSM-5/MOR为共生分子筛形态,且ZSM-5/MOR重量比例为76 / 34;化学分析测得其中Mg含量(质量分数)为0.61%,UV-Raman紫外拉曼光谱与STM球差电镜显示Mg以单原子离子形式的高分散状态存在于杂化分子筛,ICP与XRF的表征结果表明,Mg金属-杂化MOR/ZSM-5分子筛的硅铝比为36。
实施例5
将43.2 g 硫酸铝、78 .4g氯化钠溶解在340 mL去离子水中,完全溶解后制备得到铝源溶液。然后将200 .3g质量分数为27%的水玻璃中充分混合形成硅源溶液与100mL去离子水充分混合形成硅源溶液,然后将100 .5g的去离子水、20 mL乙胺与100 .1g的水玻璃作为釜底料,在剧烈搅拌的条件下,向釜底料中同时滴加上述的铝源溶液和硅源溶液,完成成胶,再用乙胺和氨水调节pH至11.2。最终形成的凝胶中的摩尔组成为6 Na2O:Al2O3:35SiO2:1180 H2O。然后加入含1.2 g氯铂酸与EDTA的络合物溶液,并加入5克ZSM-5晶种和12 gMOR晶种。室温搅拌12小时后转移至2 L的高压水热合成釜中,然后升温至140℃,晶化72 h后,然后将反应釜升温至180℃,继续晶化48 h。所得到的晶化产物,经去离子水洗涤、干燥、540℃焙烧后,获得Pt金属-杂化ZSM-5/MOR/Y分子筛;TEM透射电镜与XRD衍射仪表征分析显示Pt-ZSM-5/MOR/Y分子筛中的ZSM-5/MOR/Y为共生分子筛形态,且ZSM-5/MOR/Y重量比例为71 / 23/6;化学分析测得其中Pt含量(质量分数)为0.32%,UV-Raman紫外拉曼光谱与STM球差电镜显示Pt以单原子金属形式的高分散状态存在于杂化分子筛。上述焙烧后Pt-ZSM-5/MOR/Y分子筛使用铵盐使用8.0wt%醋酸铵水溶液在50℃下进行4 h交换处理,并重复3次,得到铵型Pt-ZSM-5/MOR/Y金属杂化分子筛, ICP与XRF的表征结果表明,Pt-ZSM-5/MOR/Y分子筛的硅铝比为39。
实施例6
将61.2 g 铝酸钠、51.6 g氯化钠溶解在430 mL去离子水中,完全溶解后制备得到铝源溶液。然后将200.3 g的硅酸钠完全溶解在450克去离子水中,形成硅源溶液。然后将200 .4g的去离子水作为釜底料,在剧烈搅拌的条件下,向釜底料中同时滴加上述的铝源溶液和硅源溶液,完成成胶,再用乙胺和氨水调节pH至11.2。最终形成的凝胶中的摩尔组成为9.7 Na2O:Al2O3:21 SiO2:1180 H2O。然后加入3.8 g 氯化镧和3.3g 氯化铈与EDTA的络合物溶液,并加入30.2克Y分子筛晶种。室温搅拌12小时后转移至2 L的高压水热合成釜中,然后升温至90℃,晶化10 h后,然后将反应釜升温至180℃,继续晶化72 h。所得到的晶化产物,经去离子水洗涤、干燥、焙烧后,获得La、Ce金属-杂化MOR/Y分子筛;TEM透射电镜与XRD衍射仪表征分析显示LaCe-MOR/Y分子筛中的MOR/Y为共生分子筛形态,且MOR/Y重量比例为87 /13;化学分析测得其中La含量(质量分数)为0.87%、Ce含量(质量分数)为0.61%,UV-Raman紫外拉曼光谱与STM球差电镜显示La、Ce以单原子离子和团簇金属氧化物形式的高分散状态存在于杂化分子筛。上述焙烧后LaCe-MOR/Y分子筛使用铵盐使用6.0wt%碳酸铵水溶液在40℃下进行5h交换处理,并重复3次,得到铵型LaCe-MOR/Y金属杂化分子筛。ICP与XRF的表征结果表明,LaCe-MOR/Y分子筛的硅铝比为36。
实施例7
将245.1 g铝酸钠、186.9 g氢氧化钠、150.2 g氢氧化钾溶解于1800 g去离子水中,形成铝源溶液,然后将660.2克硅酸钠充分溶解于750毫升去离子水中,作为硅源溶液。然后将上述的硅源溶液在剧烈的搅拌下,逐滴加入上述铝源溶液,形成凝胶,然后加入83.8g六亚甲基四胺,然后用氨水调节pH至11。最终形成凝胶中的摩尔组成为3.7 Na2O:Al2O3:24.6 SiO2:1300 H2O。然后加入65.8 g的磷钨酸钠,再加入30 g MCM-56晶种,剧烈搅拌以混合均匀,然后室温搅拌6小时后转移至5 L的高压水热合成釜中,然后升温至85℃,停止搅拌,静态晶化6 h后,将反应釜升温至160℃,继续晶化96 h。所得到的晶化产物,经去离子水洗涤、干燥、570℃焙烧后,获得W金属-杂化Y/MCM-56分子筛;TEM透射电镜与XRD衍射仪表征分析显示W-Y/MCM-56分子筛中的MOR/Y为共生分子筛形态,且Y/MCM-56重量比例为61 /39;化学分析测得其中W含量(质量分数)为8.6%,UV-Raman紫外拉曼光谱与STM球差电镜显示W以团簇金属氧化物形式的高分散状态存在于杂化分子筛。ICP与XRF的表征结果表明,W金属-杂化Y/MCM-56分子筛的硅铝比为27。
实施例8
将42.7 g 硫酸铝、1.8 g氯化钠溶解在400 mL去离子水中,完全溶解后制备得到铝源溶液。然后将300 g质量分数为40%的硅溶胶与160mL去离子水充分混合形成硅源溶液,然后将180 g的氨水作为釜底料,在剧烈搅拌的条件下,向釜底料中同时滴加上述的铝源溶液和硅源溶液,完成成胶,再用乙胺和氨水调节pH至11.08。最终形成的凝胶中的摩尔组成为0.17 Na2O:Al2O3:31 SiO2:1378 H2O。然后加入9.4 g乙酰丙酮镍,并加入20克ZSM-5晶种。室温搅拌12小时后转移至2 L的高压水热合成釜中,然后升温至120℃,晶化72 h后,然后将反应釜升温至180℃,继续晶化82 h。所得到的晶化产物,经去离子水洗涤、干燥、520℃焙烧后,获得Ni金属-杂化MOR/ZSM-5分子筛;TEM透射电镜与XRD衍射仪表征分析显示Ni-MOR/ZSM-5分子筛中的MOR/ZSM-5为共生分子筛形态,且MOR/ZSM-5重量比例为68/ 32;化学分析测得其中Ni含量(质量分数)为0.47%,UV-Raman紫外拉曼光谱与STM球差电镜显示Ni以单原子离子形式的高分散状态存在于杂化分子筛。ICP与XRF的表征结果表明,Ni金属-杂化MOR/ZSM-5分子筛的硅铝比为36。
实施例9
分别将实施例5得到铵型Pt-ZSM-5/MOR/Y金属杂化分子筛、实施例6得到铵型LaCe-MOR/Y金属杂化分子筛,按金属杂化分子筛70wt% /氧化铝30wt%的比例用4wt%硝酸助剂成型,并在540℃焙烧制成催化剂记为Cat--Pt-ZSM-5/MOR/Y,Cat--LaCe-MOR/Y;按同样分子筛晶相比例用单独的ZSM-5、MOR、Y三种铵型分子筛混合均匀,并用氯铂酸浸渍相同含量的Pt后,以相同方式成型、540℃焙烧制成催化剂记为Cat--Pt+ZSM-5+MOR+Y;按实施例5同样操作(除了未引入LaCe外)合成得到共生分子筛MOR/Y(晶相比例也实施例5相同),再用硝酸镧与硝酸铈浸渍相同含量的LaCe后,以相同方式成型、540℃焙烧制成催化剂记为Cat--LaCe+MOR/Y;按同样分子筛晶相比例用单独的MOR、Y二种铵型分子筛混合均匀,并用硝酸镧与硝酸铈浸渍相同含量的LaCe后,以相同方式成型、540℃焙烧制成催化剂记为Cat--LaCe+MOR+Y。
采用固定床反应器,分别装入上述5种催化剂颗粒20g,以甲苯/乙苯重量比 2/1为原料,在载气氢气压力1.0MPa、355℃、进料重量空速3.0h-1条件下进行甲苯歧化与乙苯脱烷基反应催化活性评价,其中;上述5种催化剂的反应转化率如下表所示。
甲苯歧化与乙苯脱烷基反应催化活性评价结果
从上表甲苯歧化与乙苯脱烷基反应催化活性评价结果可见:由金属杂化分子筛制成催化剂Cat--Pt-ZSM-5/MOR/Y、Cat--LaCe-MOR/Y的甲苯转化率和乙苯转化率均显著高于单独铵型分子筛混合并用溶液浸渍金属制成催化剂Cat--Pt+ZSM-5+MOR+Y、Cat--LaCe+MOR+Y,也明显优于使用共生分子筛MOR/Y加上溶液浸渍金属制成催化剂Cat--LaCe+MOR/Y。由此可见,该金属杂化分子筛具有高分散金属活性与更强的酸性质,在芳烃歧化、芳烃脱烷基反应催化上体现出更强的催化活性优势与更好的技术经济性。
另一方面,从200小时连续反应催化稳定性上也可看到金属杂化分子筛制成催化剂Cat--Pt-ZSM-5/MOR/Y明显优于分子筛混合与浸渍金属制成催化剂Cat--Pt+ZSM-5+MOR+Y;金属杂化分子筛催化剂Cat--LaCe-MOR/Y也优于金属浸渍共生分子筛催化剂Cat--LaCe+MOR/Y。表明了金属杂化分子筛的金属成份被分隔固定在分子筛晶体内,不易在连续反应过程中发生金属聚集问题,而能保持较好的连续反应中催化剂性能的稳定性。
实施例10
将将实施例8在低Na含量凝胶条件下合成得到Ni金属-杂化MOR/ZSM-5分子筛,经过ICP分析显示Ni-MOR/ZSM-5的Na含量仅为0.07%,所以在对Ni-MOR/ZSM-5分子筛不做铵盐交换的条件下,直接与大孔纳米氧化铝、田菁粉按照质量比70/30/5进行混合、捏合、挤条、焙烧,制备得到Ni-MOR/ZSM-5分子筛成型颗粒。然后在上述催化剂颗粒的基础上,采用等体积Mo、La的硝酸盐溶液浸渍的方法,负载4.1%的Mo和2.2%La,制备得到Mo、La+Ni-MOR/ZSM-5分子筛催化剂。将制得的催化剂装填到固定床反应器中,以苯与C9为原料,苯/C9重芳烃的质量比为43/57,在反应温度385 ℃,液相空速3.0 h-1,氢烃比3.0的条件下考评其催化性能,其结果如下:转化率50.8%,收率92.3%,二甲苯产物溴指数为13 mgBr/100g,表现出优异的苯与重芳烃烷基转移反应性能。
Claims (22)
1.一种金属杂化共生分子筛,其特征在于:所述的金属杂化共生分子筛由至少一种金属和两种微孔分子筛形成的共生分子筛所构成。
2.根据权利要求2所述的一种金属杂化共生分子筛,其特征在于:所述的金属杂化共生分子筛中的金属以团簇或单原子状态位于共生分子筛晶粒内部和表面,并以金属、金属氧化物和/或离子状态存在。
3.根据权利要求2所述的一种金属杂化共生分子筛,其特征在于:所述的金属杂化共生分子筛中的金属包含Pd、Pt、Ru、Ni、Cu、Au、Mo、Co、La、Ce、Zr、Sn、Ti、W、Cr、V、Zn、Mg、Ca、Bi、Re中的一种或多种。
4.根据权利要求3所述的一种金属杂化共生分子筛,其特征在于:所述分子筛中的金属其中金属优选自Pd、Pt、Ni、Mo、Co、La、Ce、Sn、Ti、W、Zn、Re中的一种或多种。
5.根据权利要求3所述的一种金属杂化共生分子筛中的金属,其特征在于:所述分子筛中金属所占金属杂化共生分子筛的质量分数为0.01%~10.0%。
6.根据权利要求2所述的一种金属杂化共生分子筛,其特征在于:所含的共生分子筛构成为ZSM-12、ZSM-5、MOR、Beta、MCM-22、Y分子筛中的至少二种或几种。
7.根据权利要求2所述的一种金属杂化共生分子筛,其特征在于:所含的共生分子筛的硅铝比为5~200。
8.根据权利要求7所述的一种金属杂化共生分子筛,其特征在于:其硅铝比优选为15~100。
9.一种金属杂化共生分子筛水热合成方法,其特征在于:所述的金属杂化共生分子筛是通过在共生分子筛水热合成凝胶中掺入金属前驱体化合物,使金属直接与共生分子筛结合形成整体晶体结构的方式合成制得。
10.根据权利要求9所述一种金属杂化共生分子筛水热合成方法,其特征在于:所述合成凝胶中掺入金属的方法中,所述的金属前驱体化合物,可以选择是含有金属的胶体溶液、络合物溶液或盐溶液。
11.根据权利要求10所述一种金属杂化共生分子筛水热合成方法,其特征在于:所述的金属前驱体化合物,优选自含有金属的粒径小于3 纳米胶体溶液,或选自含有金属的EDTA、乙酰丙酮、酒石酸等其它不含硫元素的络合物溶液。
12.根据权利要求9所述一种金属杂化共生分子筛水热合成方法,其特征在于:所述的合成凝胶中掺入金属的方法中,所述的金属杂化共生分子筛采用分段晶化的方法进行制备。
13.根据权利要求12一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法,是将硅源、铝源、模板剂、晶种、pH调节剂、水、金属前驱体化合物溶液混合形成凝胶后,在低温下先完成预晶化处理, 并使金属前驱体化合物均匀分解,然后置于高温下完成晶化过程;
晶化所得产物经过过滤、洗涤、焙烧后得到金属杂化共生分子筛成品,或者可以焙烧后选用铵盐进行交换处理。
14.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述凝胶具有下列摩尔组成(0.05~10)Na2O:(1.0)Al2O3:(3~220)SiO2:(720~3200)H2O。
15.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述的硅源为硅溶胶、水玻璃、二氧化硅、白炭黑、硅酸钠、正硅酸四乙酯中的一种或几种。
16.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述的铝源为铝酸钠、拟薄水铝石、氢氧化铝、硝酸铝、硫酸铝、异丙醇铝中的一种或几种。
17.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述的模板剂为四丙基氢氧化铵、乙胺、三乙胺、四乙基溴化铵、四乙基氢氧化铵、四丙基溴化铵、正丁胺、六亚甲基亚胺中的一种或几种。
18.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述的pH调节剂为烧碱、纯碱、氨水、盐酸、硝酸、硫酸中的一种或几种。
19.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述的低温阶段温度为50~120℃,晶化4~48 h。
20.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述的高温阶段温度为160~200℃,晶化36~72 h。
21.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,所述的焙烧温度为500~600℃,在空气气氛下焙烧2~8 h。
22.根据权利要求13一种金属杂化共生分子筛水热合成方法,其特征在于:所述的分段晶化的方法中,焙烧后选用铵盐进行交换处理,铵盐可选自醋酸铵、甲酸铵、碳酸铵或草酸铵。
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