CN105579398A - 用于制备沸石β的方法及其用途 - Google Patents
用于制备沸石β的方法及其用途 Download PDFInfo
- Publication number
- CN105579398A CN105579398A CN201380064184.1A CN201380064184A CN105579398A CN 105579398 A CN105579398 A CN 105579398A CN 201380064184 A CN201380064184 A CN 201380064184A CN 105579398 A CN105579398 A CN 105579398A
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- China
- Prior art keywords
- pdadma
- zeolite beta
- sio
- silicon source
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 112
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000004411 aluminium Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 230000029936 alkylation Effects 0.000 claims description 12
- 238000005804 alkylation reaction Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- -1 benzylalcohol, phenyl aldehyde Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 8
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 37
- 238000003786 synthesis reaction Methods 0.000 description 32
- 230000008569 process Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 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 1
- 239000002028 Biomass Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 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
- 239000002904 solvent Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
制备沸石β的方法,所述方法包括从包含模板、硅源和铝源的溶液中结晶沸石β,其中所述模板为包含可电离的聚二烯丙基二甲基铵(PDADMA)阳离子结晶的聚合化合物。此外,本发明提供了由此制得的沸石β在用于烃类转化的催化剂中的用途。
Description
技术领域
本发明涉及一种用于制备沸石β的新型方法,更具体地涉及制备具有复合孔隙结构的沸石β的新型方法,还涉及如此制得的沸石β在用于烃类转化的催化剂中的用途。
背景技术
在沸石领域中,具有复合孔隙结构的沸石意指沸石除了其原始孔隙结构之外掺入另一孔隙结构以具有复合孔隙结构,由此所述沸石具有不同的孔隙结构和改进的孔隙率,以及不同的质量传递能力和催化活性。
自从具有复合孔隙结构的MCM-41沸石分子筛在1992年由来自美国的MobilCompany合成,并发现其具有快速质量传递的能力和用于烃类转化的高催化活性[参见Kresge,C.T.,Leonovicz,M.E.,Roth,W.,J.,Vartuli,J.S.Nature353,(1992),710],具有复合孔隙结构的沸石已收到越来越多的关注,并且已成功将复合孔隙结构赋予越来越多的沸石,因此沸石被赋予用于广泛工业用途的更多的可能性。
具有复合孔隙结构的沸石β为如下沸石:除了其原始微孔结构之外,介孔结构被掺入其中,使得沸石β具有同时包含微孔结构和介孔结构的复合孔隙结构,由此沸石β具有改进的质量传递效率和用于烃类转化的催化活性。
Ryoo等人已开发了一种用于合成同时包含介孔和微孔的沸石的双官能表面活性剂,由此产生沸石纳米片材或介孔沸石。然而,所述双官能表面活性剂成本高,使得其工业应用较不可行。因此,本领域仍然需要改进具有复合孔隙结构的沸石β的合成。
为了使具有复合孔隙结构的沸石β可在商业上使用,在中国专利申请CN1749162A中,发明人已通过使用聚季铵盐-6(聚二烯丙基二甲基氯化铵)和TEAOH(四乙基氢氧化铵)的组合作为模板而成功合成了具有复合孔隙结构的沸石β(参见其中的实施例2和图8-9)。
根据组合模板的基于本领域的常规概念的这种合成途径,有机小分子模板(即四乙基氢氧化铵(TEAOH))用于形成微孔,且有机高分子模板(即聚季铵盐-6)用于形成介孔。因此,两种有机模板必须极好地彼此匹配,否则一些无定形多孔材料可能易于在合成的沸石中形成。因此,这种组合模板使得具有复合孔隙结构的沸石β的合成略为复杂,尽管其比已用于商业应用的Ryoo等人的合成更可行。
在这种情况下,本发明人现在已出乎意料地发现,具有有利性质的沸石β,更具体地具有复合孔隙结构的沸石β可通过使用包含可电离的聚二烯丙基二甲基铵(PDADMA)阳离子的聚合化合物(如聚季铵盐-6))作为在所述沸石β的制备过程中存在的仅有的模板而成功合成。考虑到这种聚合化合物(如聚季铵盐-6)作为商业试剂比TEAOH便宜得多,本发明使得具有复合孔隙结构的沸石β的合成更简化且具有降低的成本,因此促进具有复合孔隙结构的沸石β在广泛的工业应用中使用。
发明内容
因此,本发明提供了一种用于制备沸石β,更具体地用于制备具有复合孔隙结构的沸石β的方法。该方法可通过常规水热合成进行,但不同于现有技术中的组合模板,在其制造过程中仅存在单个类型的模板,这产生具有有利性质的沸石β,更具体地产生具有沸石β的复合孔隙结构的组合的微孔结构和介孔结构的沸石β。
具体地,本发明提供了一种用于制备沸石β的方法,所述方法包括从包含模板、硅源和铝源的溶液中结晶沸石β,其中所述模板为包含可电离的聚二烯丙基二甲基铵(PDADMA)阳离子的聚合化合物。更具体地,制备过程为使用PDADMA作为模板的水热结晶,其中作为SiO2计算的硅源与作为阳离子PDADMA单体计算的聚合化合物之间的摩尔比SiO2/PDADMA为1-10,优选为3-8,最优选为5-7,作为SiO2计算的硅源与作为碱金属氧化物M2O计算的碱源之间的摩尔比SiO2/M2O为1-10,优选为3-8,最优选为4-6。该制备过程优选在150-230℃,优选170-200℃的温度下进行48-312h,优选60-240h,最优选72-120h的时间。
根据本发明,其中铝源和水可以以本领域中的常规量使用,然而,优选的是作为SiO2计算的硅源与作为Al2O3计算的铝源之间的摩尔比SiO2/Al2O3为20-100,优选为30-80,最优选为40-55,且水与作为SiO2计算的硅源之间的摩尔比H2O/SiO2为10-80,优选为25-65,最优选为40-50。
根据本发明,其中水热结晶可常规进行,具体地可通过顺序地混合、胶凝和结晶而进行。更具体地,根据本发明,在水热结晶过程中,首先将铝源和碱源溶解于水中,添加聚合PDADMA化合物并搅拌0.2-1.5h,优选0.3-1.0h的时间以形成澄清溶液;将硅源添加至溶液中并搅拌6-48h,优选12-24h的时间以形成凝胶;将所述凝胶转移至高压釜以结晶。
根据本发明,其中在水热结晶之后,可常规地处理所得产物以获得具有复合孔隙结构的最终沸石β。具体地,根据本发明,可将通过水热结晶而获得的产物顺序地过滤、干燥和煅烧。更具体地,通过水热结晶而获得的产物可在环境温度至40℃,优选环境温度至30℃的温度下过滤,在80-120℃,优选90-110℃的温度下干燥,并在400-700℃,优选500-600℃的温度下煅烧3-10h,优选4-8h的时间。
根据本发明,其中硅源可为本领域常规使用的任意硅源,具体地,硅源可选自氧化硅(如硅胶、硅溶胶、石英、白炭黑和粘土);硅酸;硅酸酯(如硅酸甲酯、硅酸乙酯和硅酸丙酯);和硅酸盐(如硅酸钠、硅酸钾和硅酸铝)。
根据本发明,其中铝源可为本领域常规使用的任意铝源,具体地,铝源可选自铝酸盐(如铝酸钠和铝酸钾);铝盐(如异丙醇铝、硅酸铝、硫酸铝、硝酸铝和氯化铝);铝矿物质(如勃姆石和拟薄水铝石);和铝。
根据本发明,其中碱源可为本领域常规使用的任意碱源,具体地,碱源可选自碱金属和碱土金属的氧化物、氢氧化物、碳酸盐和碳酸氢盐,优选选自碱金属氧化物、氢氧化物、碳酸盐和碳酸氢盐,特别地选自氧化钠、氧化钾、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠和碳酸氢钾,最优选选自氢氧化钠和氢氧化钾。
根据本发明,硅酸钠和铝酸钠也可用作碱源。因此,根据本发明,硅酸钠可同时用作硅源和碱源,铝酸钠可同时用作铝盐和碱源。
包含可电离的聚二烯丙基二甲基铵(PDADMA)阳离子的聚合化合物为能够提供PDADMA阳离子的化合物。据信该聚合化合物在沸石合成过程中提供复合孔隙结构。根据本发明,模板可为能够在沸石合成过程中提供PDADMA阳离子的任意聚合化合物。在本文中,聚合化合物指包含聚合阳离子和小阴离子的化合物,更具体地指包含PDADMA阳离子和小阴离子的化合物(其简称为聚合PDADMA化合物)。
根据本发明,其中起模板作用的聚合PDADMA化合物可以以本领域的常规分子量范围使用,具体地,PDADMA盐可具有1×105-5×105,优选1×105-3×105,最优选1×105-2×105的分子量。
根据本发明,起模板作用的聚合PDADMA化合物的例子可包括PDADMA盐或氢氧化物,优选PDADMA盐,且所述PDADMA盐可为PDADMA卤化物,优选PDADMA氯化物、PDADMA溴化物和PDADMA碘化物,最优选PDADMA氯化物。
根据本发明,其中当模板为PDADMA盐时,其可以以固体含量为10-60wt%,优选15-45wt%的水溶液的形式提供。
不希望受限于任何特定的理论,发明人认为在特定合成条件下,在沸石β的复合孔隙结构的形成过程中,阳离子PDADMA的小的季铵头部可引导微孔的形成,因为类似的小的季铵阳离子为用于合成常规沸石β的一般模板,具有相对大的分子量的阳离子PDADMA部分可引导介孔的形成。因此,这种具有特定季铵头部的起模板作用的聚合化合物具有同时形成微孔和介孔的两个功能,并类似于Ryoo等人的精巧(delicated)表面活性剂,但具有明显降低的成本。此外,仅使用起模板作用的聚合PDADMA化合物比发明人之前的中国专利说明书CN1749162A中的组合模板更简单。
根据本发明,合成的沸石β具有改进的性质。具体地,相比于常规沸石β,目前合成的沸石β具有可相比的Si/Al比,高得多的BET表面积和高得多的孔隙体积以及优良的水热稳定性,所有这些性质对于沸石β用于工业应用中是极为关键的。
在本文中,发明人已发现根据本发明的沸石β尤其适于在用于烃类转化的催化剂中使用,具体地,由于其特别高的比表面积和高孔隙体积,这种沸石β不仅可在用于加氢裂化轻质烃类的催化剂中使用,还可在用于转化大分子烃类的催化剂中使用。
因此,本发明也提供了一种包含目前合成的沸石β的烃类转化催化剂。更具体地,烃类转化催化剂包含5-95wt%的耐火氧化物粘结剂、5-95wt%的根据本发明制得的沸石β,和0.01-30wt%的催化活性金属,所有百分比均基于干燥催化剂的总量。
关于本发明的烃类转化催化剂,粘结剂可为任意耐火氧化物。优选地,粘结剂选自氧化硅、氧化铝、氧化硅-氧化铝和氧化钛。催化活性金属优选选自钼、钨、镍、钴、铂和钯。
本发明的烃类转化催化剂可以以本领域技术人员已知合适的任何方式(如通过共研碎和挤出)制得。优选地,催化剂通过如下方式制得:共研碎或挤出根据本发明制得的沸石β和粘结剂,随后用含有催化活性金属的溶液浸渍挤出物。最终催化剂通过随后的干燥、煅烧和任选的硫化而获得。
本发明还提供了一种用于通过在本发明的烃类转化催化剂的存在下在升高的温度和升高的压力下使烃类原料与氢接触而加氢裂化烃类的过程。这种过程的例子包括单阶段加氢裂化、两阶段加氢裂化和连续流(series-flow)加氢裂化。
根据本发明,加氢裂化过程可在250-500℃的反应温度和3×106至3×107Pa,更优选8×106至2.0×107Pa的总压力(在反应器入口处)下常规进行。当加氢裂化过程在例如至多1.2×107Pa的低压下进行时,其可称为‘温和加氢裂化’。
可用于本发明的过程中的烃类进料可在广泛沸腾范围内变化。它们包括常压瓦斯油、焦化瓦斯油、真空瓦斯油、脱沥青油、获自Fischer-Tropsch合成过程的石蜡、长和短的渣油、催化裂化的循环油、热裂化或催化裂化的瓦斯油,和任选地源自焦油砂的合成原油、页岩油、渣油改质过程和生物质。也可使用各种烃油的组合。然而,通常最适用于本发明的过程的原料为通过裂化或分馏处理原料而获得的轻质原料或馏分。这种原料包括常压和真空瓦斯油、通过裂化过程而形成的瓦斯油、循环油,和类似沸腾范围的原料。原料的沸腾范围通常为大约90-650℃。
此外,本发明也涉及利用目前合成的沸石β的大分子烃类转化,所述大分子烃类转化包括聚乙烯的热解、苯与苄醇的烷基化(ABB)、苯甲醛与羟苯乙酮的缩合(CBH),以及苯酚与叔丁醇的烷基化(APT)。
对于大分子烃类转化,目前合成的沸石β可达到比常规沸石β高得多的催化活性和转化率。例如,对于在两种沸石上的LDPE热解,当转化率为10%和50%时,目前合成的沸石β的热解温度分别比常规沸石β的热解温度低60℃和23℃,据信这种改进是由于在目前合成的具有复合孔隙结构的沸石β中存在介孔(参见图4)。
附图说明
现在参照附图进一步描述本发明,其中:
图1显示了通过本发明合成的沸石产物的X射线衍射(XRD)图谱;
图2显示了通过本发明合成的沸石产物的等温氮气吸收-解吸曲线;
图3a-3d显示了通过本发明合成的沸石产物的TEM图像,其中图3a和图3b为低放大率图像,图3c和3d为高分辨率图像,且在图3b的左下部***的是沸石粒子的电子衍射图像;
图4显示了在β-MS(根据本发明的沸石β)和β(常规沸石β)上以及在无任何催化剂的情况下(空白)转化率相对于PDPE热解的温度的曲线,其中转化率由热重数据确定;和
具体实施方式
在本发明中,涉及如下测量:
Si/Al比通过PW1400X射线荧光光谱仪XRF分析确定;
XRD谱通过使用CuKα()辐射的RigakuX射线衍射仪测得;
等温氮气吸收-解吸曲线使用MicromeriticsASAP2020M和3020M***在-196℃下测得,其中样品在测量之前在150℃下脱气10h;
TEM图像在200kV下操作的JEOLJEM-2100F电子显微镜上和在300kV下操作的JEOLJEM-3010仪器上获得;
介孔的孔隙尺寸分布使用Barrett-Joyner-Halenda(BJH)模型计算;且
热重分析(TG)和示差热分析(DTA)以10℃/min的加热速率在空气中使用SDTQ600V8.2Build100仪器进行。
现在参照具体实施例描述本发明,提供所述具体实施例仅为说明本发明,而不是以任何方式限制本发明。
实施例
在该实施例中,所有的反应试剂具有工业级,其中:
模板为购自Sigma-AldrichCompany,Ltd.(USA)的聚二烯丙基二甲基氯化铵(固体含量为20wt%的水溶液,且分子量为1×105-2×105);
硅源为购自ShenyangChemicalCo.的热解法二氧化硅;
碱源为NaOH,铝源为NaAlO2,两者均购自SinopharmChemicalReagentCo.;
苯、苄醇、苯甲醛、2-羟苯乙酮、苯酚、叔丁醇和十二烷购自AladdinIndustrialCo(China);且
低密度聚乙烯(LDPE)购自AlfaAesar。
具有复合孔隙结构的沸石β的合成
在该实施例中,根据本发明的沸石β的单晶通过使用PDADMA氯化物作为模板而合成,其中作为SiO2计算的硅源、作为阳离子PDADMA单体计算的模板,作为Al2O3计算的铝源,作为Na2O计算的碱源和H2O以45SiO2/7.5PDADMA/Al2O3/10Na2O/2258H2O的摩尔比使用。
具体地,将0.08gNaA1O2和0.3gNaOH溶解于12.1mL去离子水中,然后添加2.0gPDADMA氯化物(基于固体含量为20wt%的水溶液计算),并持续搅拌约0.5h以形成澄清溶液;然后,将0.935g热解法二氧化硅添加至所述澄清溶液中,并持续搅拌12-24h以形成凝胶;将所得凝胶转移至高压釜,以在约180℃下结晶约96h;最后,在室温下过滤所得结晶产物,在约100℃下干燥,并在约550℃下煅烧约5h以去除模板,由此获得沸石产物β-MS。
产物的表征、确定和性质
分别测量沸石产物β-MS的XRD谱、等温氮气吸收-解吸曲线和TEM图像。具体地:
XRD谱示于图1中。可以看出,所示图谱为典型的沸石β,因此,可以确定目前合成的产物实际上为沸石β;
等温氮气吸收-解吸曲线示于图2中。可以看出,等温氮气吸收-解吸曲线在0.50<P/P0<0.90的相对压力下显示出滞后回线,由此可确定在目前合成的沸石β中介孔的存在。
TEM图像示于图3a-3d中,其中低放大率图像(图3a和3b)显示样品中明显的介孔,因此进一步确定目前合成的沸石β具有复合孔隙结构;其中高分辨率TEM图像(图3c和3d)显示在相同方向上极为有序的介孔,这与沸石β的单晶的特性良好一致,因此确定目前合成的具有复合孔隙结构的沸石β为其单晶,此外,这方面可通过如下得以证实:在图3b的左下部***的沸石β粒子的电子衍射为单组衍射图谱,这表明沸石β粒子为单晶而不是纳米晶体聚集体。
最后,对于目前合成的具有复合孔隙结构的沸石β,通过进一步分析和测量获得如下性质,即10.2的Si/Al比,724m2/g的BET表面积,0.90cm3/g的孔隙体积,和7nm的BJH孔隙尺寸分布的计算中心值。
水热稳定性的测试
在暴露于700℃下的100%蒸气达2h之后,合成的沸石产物β-MS具有538m2/g的BET表面积,0.87cm3/g的孔隙体积,和11.4nm的BJH孔隙尺寸分布的计算中心值。相比于上述初始数据,可以知晓目前合成的具有复合孔隙结构的沸石β-MS具有良好的水热稳定性,即甚至在水热处理之后保持高的BET表面积和大的孔隙体积。因此,目前合成的具有复合孔隙结构的沸石β具有用于工业应用的良好性质。
催化能力的测试
测试目前合成的具有复合孔隙结构的沸石β-MS相比于常规的沸石β的催化能力,常规沸石β购自南开大学,并具有12.2的Si/Al比,587m2/g的BET表面积和0.36cm3/g的孔隙体积,并在水热处理之后(即在暴露于700℃下的100%蒸气达2h之后)具有487m2/g的BET表面积和0.36cm3/g的孔隙体积,换言之,该常规的沸石β具有良好的水热稳定性,并且也适用于工业应用。表1显示了关于目前合成的具有复合孔隙结构的沸石β-MS和常规的沸石β在水热处理前后的性质的概要。
表1
用于催化能力的测试中的所有沸石样品均为氢形式。为此目的,沸石样品在80℃下与1MNH4NO3离子交换,然后在500℃下煅烧5h,该工序重复两次,由此获得氢形式的具有复合孔隙结构的沸石β-MS和常规沸石β。
在本文,所获得的氢形式的具有复合孔隙结构的沸石β-MS和常规沸石β在大分子烃类转化(如低密度聚乙烯(LDPE)热解、苯与苄醇的烷基化(ABB)、苯甲醛与羟苯乙酮的缩合(CBH),以及苯酚与叔丁醇的烷基化(APT))中使用。
首先,在50cm3/min的氮气流和以10℃/min的速率从30℃跃升至600℃的反应温度下,在HENVENHCT-3(Beijing)差热天平中进行低密度聚乙烯(LDPE)热解,其中将聚合物粉末和沸石小心称重,并在差热天平的α-Al2O3坩埚中以10:1的质量比紧密混合。图4显示了在β-MS(具有复合孔隙结构的沸石β)和β(常规沸石β)上以及在无任何催化剂的情况下(空白)转化率相对于PDPE热解的温度的曲线,其中转化率由LDPE的热重数据确定。
如可由图4知晓,目前合成的具有复合孔隙结构的沸石β-MS具有比常规β沸石高得多的催化活性,具体地,具有复合孔隙结构的沸石β-MS可在相对低的反应温度下达到相对高的转化率。当然,沸石β-MS和沸石β相比于无任何催化剂的情况(在图4中显示为空白)显示明显的催化活性。
此外,在使用苯与苄醇的烷基化(ABB)、苯甲醛与羟苯乙酮的缩合(CBH),以及苯酚与叔丁醇的烷基化(APT)中(它们的反应式显示于图5中),所获得的产物由具有火焰离子化检测器(FID)的气相色谱Shimazu2010C进行分析,其中使用柱DB-1(30m),火焰离子化检测器(FID)在280℃的温度下,且分离的产物通过1HNMR技术确定。
所有上述三个反应在配备冷凝器和磁力搅拌器的三颈圆底烧瓶中进行,其中反应温度以10℃/min的加热速率由80℃的初始值跃升至280℃的最终值。在所有三个反应中,需要高于800rpm的搅拌速率和小于400目的催化剂粒子。
具体地,苯与苄醇的烷基化(ABB)通过在约80℃下混合0.02g催化剂与57mmol苯和2.9mmol苄醇达约5h的时间而进行;苯甲醛与2-羟苯乙酮的缩合(CBH)通过在约150℃下混合0.10g催化剂与14mmol苯甲醛和7mmol2-羟苯乙酮达约18h的时间而进行;且苯酚与叔丁醇的烷基化(APT)通过在约100℃下混合0.15g催化剂与5mmol苯酚、10mmol叔丁醇和10ml环己烷溶剂达约4h的时间而进行。
每个反应在两个催化剂上的转化率显示于表2中。
表2
如可由表2中的数据知晓,就苯与苄醇的烷基化(ABB)、苯甲醛与羟苯乙酮的缩合(CBH),以及苯酚与叔丁醇的烷基化(APT)而言,目前合成的具有复合孔隙结构的沸石β-MS达到比常规沸石β高得多的转化率。
因此,当用作用于大分子烃类转化的催化剂时,目前合成的具有复合孔隙结构的沸石β比常规沸石β好得多。
Claims (13)
1.一种用于制备沸石β的方法,所述方法包括从包含模板、硅源和铝源的溶液中结晶沸石β,其中所述模板为包含可电离的聚二烯丙基二甲基铵(PDADMA)阳离子的聚合化合物。
2.根据权利要求1所述的方法,其中所述沸石β通过包含PDADMA和硅源的溶液的水热结晶制得,所述PDADMA和所述硅源以作为SiO2计算的硅源与作为阳离子PDADMA单体计算的聚合化合物之间的摩尔比SiO2/PDADMA为1-10存在,且作为SiO2计算的硅源与作为碱金属氧化物M2O计算的碱源之间的摩尔比SiO2/M2O为1-10。
3.根据权利要求1或2所述的方法,其中所述水热结晶在150-230℃,优选170-200℃的温度下进行48-312h,优选60-240h,最优选72-120h的时间。
4.根据权利要求1至3中任一项所述的方法,其中作为SiO2计算的硅源与作为Al2O3计算的铝源之间的摩尔比SiO2/Al2O3为20-100,优选为30-80,最优选为40-55,且水与作为SiO2计算的硅源之间的摩尔比H2O/SiO2为10-80,优选为25-65,最优选为40-50。
5.根据权利要求1至4中任一项所述的方法,其包括将所述铝源和所述碱源溶解于水中,添加聚合PDADMA化合物并搅拌0.2-1.5h,优选0.3-1.0h的时间以形成澄清溶液;将所述硅源添加至溶液中并搅拌6-48h,优选12-24h的时间以形成凝胶;并将所述凝胶转移至高压釜中以结晶。
6.根据权利要求1-5中任一项所述的方法,其中通过结晶而获得的产物顺序进行过滤、干燥和煅烧,以获得具有复合孔隙结构的最终沸石β。
7.根据权利要求1-6中任一项所述的方法,其中所述起模板作用的聚合PDADMA化合物具有1×105-5×105,优选1×105-3×105,最优选1×105-2×105的分子量。
8.根据权利要求1-7中任一项所述的方法,其中所述起模板作用的聚合PDADMA化合物为PDADMA盐,且所述PDADMA盐优选为PDADMA卤化物,更优选为PDADMA氯化物、PDADMA溴化物和PDADMA碘化物,最优选为PDADMA氯化物。
9.根据权利要求8所述的方法,其中将所述起模板作用的PDADMA盐添加至水溶液形式的制备溶液中,所述水溶液具有10-60wt%,优选15-45wt%的固体含量。
10.根据权利要求1-9中任一项所述的方法制得的沸石β在用于烃类转化的催化剂中的用途。
11.根据权利要求10所述的用途,其中所述烃类转化包括烃类化合物的加氢裂化。
12.根据权利要求10或11所述的用途,其中所述烃类转化选自聚乙烯的热解、苯与苄醇的烷基化(ABB)、苯甲醛与羟苯乙酮的缩合(CBH),以及苯酚与叔丁醇的烷基化(APT)。
13.包含根据权利要求1至9中任一项制得的具有复合孔隙结构的沸石β的催化剂。
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---|---|---|---|---|
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-
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Non-Patent Citations (5)
Title |
---|
FENG-SHOU XIAO ET AL.: "Catalytic Properties of Hierarchical Mesoporous Zeolites Templated with a Mixture of Small Organic Ammonium Salts and Mesoscale Cationic Polymers", 《ANGEWANDTE CHEMIE》 * |
KARIN MOLLER ET AL.: "Hierarchical Zeolite Beta via Nanoparticle Assembly with a Cationic Polymer", 《CHEMISTRY OF MATERIALS》 * |
LIFENG WANG ET AL.: "Hierarchical mesoporous zeolites with controllable mesoporosity templated from cationic polymers", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
SHUZHEN LIU ET AL.: "Preformed zeolite precursor route for synthesis of mesoporous X zeolite", 《COLLOIDS AND SURFACES A》 * |
XIANGJU MENG ET AL.: "Templating route for synthesizing mesoporous zeolites with improved catalytic properties", 《NANO TODAY》 * |
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EP2928827A1 (en) | 2015-10-14 |
CN103864092A (zh) | 2014-06-18 |
CN105579398B (zh) | 2018-12-18 |
EP2928827B1 (en) | 2019-02-20 |
US20160184808A1 (en) | 2016-06-30 |
WO2014090808A1 (en) | 2014-06-19 |
US9555402B2 (en) | 2017-01-31 |
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