CN107519923B - Y/EU-1/ZSM-5/ASA/heteropoly acid composite material and preparation method thereof - Google Patents
Y/EU-1/ZSM-5/ASA/heteropoly acid composite material and preparation method thereof Download PDFInfo
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- CN107519923B CN107519923B CN201610451114.7A CN201610451114A CN107519923B CN 107519923 B CN107519923 B CN 107519923B CN 201610451114 A CN201610451114 A CN 201610451114A CN 107519923 B CN107519923 B CN 107519923B
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- 239000002131 composite material Substances 0.000 title claims abstract description 149
- 238000002360 preparation method Methods 0.000 title claims abstract description 107
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 66
- 239000002808 molecular sieve Substances 0.000 claims abstract description 256
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 255
- 239000000243 solution Substances 0.000 claims abstract description 147
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 230000032683 aging Effects 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 162
- 239000011959 amorphous silica alumina Substances 0.000 claims description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 95
- 238000003756 stirring Methods 0.000 claims description 84
- 229910001868 water Inorganic materials 0.000 claims description 81
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 64
- 239000011734 sodium Substances 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- 229910052593 corundum Inorganic materials 0.000 claims description 49
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 49
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 36
- 235000019353 potassium silicate Nutrition 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 31
- 239000011541 reaction mixture Substances 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 26
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 26
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- 230000003068 static effect Effects 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 6
- -1 neopelex Chemical compound 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000008247 solid mixture Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 36
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 53
- 229910052708 sodium Inorganic materials 0.000 description 53
- 239000012452 mother liquor Substances 0.000 description 31
- 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 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005360 mashing Methods 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002023 wood Substances 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
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000033498 Non-syndromic pontocerebellar hypoplasia Diseases 0.000 description 1
- 229910020881 PMo12O40 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 208000017262 paroxysmal cold hemoglobinuria Diseases 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 208000004351 pontocerebellar hypoplasia Diseases 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000967 suction filtration Methods 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
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7846—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a Y/EU-1/ZSM-5/ASA/heteropoly acid compound containing regular mesoporesThe preparation method of the composite material comprises the following steps: firstly synthesizing a guiding agent, synthesizing a small-grain Y-type molecular sieve by adopting a hydrothermal crystallization method, then adding a surfactant, EU-1 and ZSM-5 molecular sieve slurry and an alkaline aluminum source solution into the slurry containing the molecular sieve, and washing, drying and roasting the product to obtain the mesoporous Y/EU-1/ZSM-5/ASA composite material. Then at H3PMo12‑X‑YWXLaYO40·nH2And adding a surfactant into the O heteropoly acid aqueous solution, mixing with the Y/ASA material, pulping, aging, and drying to obtain the mesoporous Y/EU-1/ZSM-5/ASA/heteropoly acid composite material.
Description
Technical field
The present invention provides a kind of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material and preparation method, first by Y molecule
Sieve, EU-1 molecular sieve, ZSM-5 molecular sieve and amorphous silica-alumina (ASA) synthesize Y/ASA composite material through in-stiu coating, then will be miscellaneous
Polyacid aqueous solution mixes with Y/EU-1/ASA composite material, is beaten, constant temperature aging, drying, and it is miscellaneous to obtain Y/EU-1/ZSM-5/ASA/
Polyacid composite material.
Background technique
Molecular sieve complex, which refers to, is incorporated in one by molecule, atom or interionic effect by molecular sieve and other materials
The composite material risen.Regular material with meso-hole structure such as MCM-41 mesopore molecular sieve is suitble to because of its biggish cellular structure
In the conversion of organic macromolecule, but its poor thermal stability, hydrothermal stability and weaker acidity limit this kind of materials
In the application of catalytic field.The research of micropore-mesopore composite material based on high stability and highly acid micro porous molecular sieve
Then there is important industrial application value.
With the continuous developing that molecular sieve catalytic is applied, the molecular sieve in single duct is no longer satisfied diversified urge
Agent prepares demand.Micro porous molecular sieve is in heterogeneous catalysis application mainly with stronger Acidity and higher structural stability
It is good at, but since micro porous molecular sieve mostly aperture is smaller, duct is elongated, and the macromolecular in reaction raw materials such as heavy oil is difficult to diffuse into
Enter to inside duct, can then reduce the utilization rate of acidic site inside micro porous molecular sieve duct, while the duct of narrow elongate in this way
Diffusional resistance is larger, and the quick diffusion for influencing reaction product molecule is overflowed, and is easy to cause drastic cracking and green coke.And mesoporous molecular
Although sieve can make up the limitation that micro porous molecular sieve is spread in reactant and reaction product, the structure of mesopore molecular sieve is steady
It is qualitative often poor, also limit its catalytic applications.
Heteropoly acid has preferable hydrogenation activity, has been applied to gasoline and diesel hydrogenation and has been hydrocracked field, but has only limited
In lab scale conceptual phase, main cause is that heteropoly acid thermal stability prepared at present is poor, is begun to after being heated to 500 DEG C or more
It decomposes, limits heteropoly acid in the application of field of hydrogenation.Simultaneously heteropoly acid itself specific surface area and Kong Rongjun it is smaller, limitation its
Catalytic activity will greatly improve its catalytic activity by loaded by heteropoly acid on the porous carriers such as aluminium oxide.
CN 200810012192 provides a kind of preparation method of Y molecular sieve/silicon dioxide composite material, by Y type molecule
Sieve, sodium hydroxide, distilled water, template and silicon source are uniformly mixed under stirring, and reaction mixture gel, each component is made
Mol ratio are as follows: (0-1.3) Na2O:(34.4-110)H2O:(0.75-11.3)SiO2: (0.046-0.7) R, R is template.It should
Gel crystallization 12-70h at 80-180 DEG C, is filtered, is washed, and hud typed composite material is obtained.Y molecular sieve is in composite material
In content in 10~30wt%, the partial size of composite material is at 2~10 μm.Y type molecular sieve is not involved in silica in this method
Outgrowth, without chemical bond between Y type molecular sieve and silica, silica cannot provide acidity, urge various
Changing can only play the role of selecting type in reaction, so the acidity of composite material can only be realized by modulation Y molecular sieve.But mesoporous is not
The multi-stage porous of rule.
Liu et al. is in document Journal of American Chemical Society (2000,122:8791-8792)
Describe a kind of method for preparing mesoporous material using Y molecular sieve secondary structure unit: first by NaOH, NaAlO2、H2O and water
Glass mixing, is made containing 27wt%SiO2With the Y molecular sieve seed-solution of 14wt%NaOH, template is introduced into seed-solution
CTAB and dilution heat of sulfuric acid, the pH value for adjusting seed-solution is 9,100 DEG C of crystallization 20h, Y points in crystallization process in seed-solution
Son sieve secondary structure unit is assembled into the composite material with hexagonal mesoporous structure, Al-MSU- under the action of template CTAB
S.The purpose is to use the assembly mesoporous material of Y type molecular sieve, but the mesoporous wall of micro--mesoporous composite material is amorphous structure,
Hydrothermal stability is poor.
Zhang etc. describes one kind in document Applied Catalysis A:General (2008,345:73-79)
Y/MCM-48 is micro--preparation method of mesoporous composite material: NaY crystal seed is added in the precursor sol of MCM-48, presoma is molten
Unclassified stores forms in liquid are as follows: 1TEOS:0.415CTAB:0.48NaOH:55H2O, after mixed liquor stirs 50 minutes, at 110 DEG C
For a period of time, suction filtration, washing obtain solid product to lower hydrothermal crystallizing, and 550 DEG C of roasting 6h obtain Y/MCM-48 in air atmosphere
Composite molecular screen.Although the mesoporous wall thickness of the MCM-48 molecular sieve of this method preparation is increased, its hole wall is still nothing
Amorphous configuration, therefore poor be still of hydrothermal stability restricts its major reason applied.
CN102000604A provides one kind using kaolin as raw material, and inorganic silicate is to add silicon source, microwave method preparation
The method of Y/MCM-41 composite molecular screen.Before adding a certain amount of sodium metasilicate synthesis Y type molecular sieve as raw material using kaolin first
Body is driven, then using cetyl trimethylammonium bromide as template, microwave method prepares composite molecular screen Y/MCM-41.The Y/ of synthesis
MCM-41 composite molecular screen has micro--mesoporous double-pore structure, and the specific surface area of sample is greater than 550m2/ g, average pore size are about
2.7nm, sample have regular hexagonal mesoporous structure.Although the MCM-41 molecular sieve hole wall of this method preparation introduces Y type
Molecular sieve secondary structure unit, but thermal stability is still short of, and collapse temperature is lower than 800 DEG C.
CN101172244 provides a kind of preparation method of montmorillonite/Y molecular sieve composite material.By by montmorillonite
Grain is uniformly mixed with Y molecular sieve gel, then carries out crystallization, and is filtered, washed and dried drying and the montmorillonite/Y molecule is made
Sieve composite material.Composite material made from the method for the present invention, while there is the structure feature of montmorillonite and Y molecular sieve, montmorillonite
With Y molecular sieve alternate, Y molecular sieve is grown on montmorillonite microballoon, but this method preparation composite material in Y molecular sieve skeleton
Sial is relatively low, and it is poor to may cause its hydrothermal stability.
CN101172243 provides a kind of preparation method of mesoporous/micropore molecular sieve composite material.The composite material is logical
It crosses to mix adobe isomery material (PCHs) with micro porous molecular sieve gel and carry out made from in-situ crystallization.Invention preparation
In composite material, micro porous molecular sieve is wrapped in adobe isomery surrounding materials, which has micro porous molecular sieve simultaneously
Crystal structure and adobe isomery material meso-hole structure, belong to porosity Composite material.Matched in composite material according to gel
It can be crystallized to obtain the micro porous molecular sieves such as Y type, ZSM-5 type, β type than difference.The stability that this method prepares composite material is poor.
CN200610165597.0 provides a kind of preparation side of nano molecular sieve/sieve and silica-sesquioxide composite catalyzing material
Method first synthesizes nano molecular sieve using directing agent method, and the precipitation step in synthesis is handled using microwave and/or ultrasonic wave,
Then the mixture aqueous solution of waterglass and silicon source is added in the slurries containing nano molecular sieve, it is 7~9.5 that acid adding, which is adjusted to pH,
Form gel；Then by gel drying, roasting to get the composite catalyzing material, wherein silicon source is selected from sodium metaaluminate or aluminum sulfate,
The particle that this method sieves products molecule is maintained at 100nm or less and nano molecular sieve therein is not easy to assemble, without
Acidic sol process and avoid molecular sieve by acid destroy.The composite material is suitable for the catalytic cracking of heavy oil macromolecular and hydrogen is added to split
Change reaction.
Landau etc. describes one in document Applied Catalysis A:General (1994,115:L7-L14)
The method of kind fabricated in situ nano molecular sieve ZSM-5 in the duct of Silica hydrogel forms 3~5 μm of partial size in the outer surface of silica gel
Zeolite, form 0.5~2 μm of partial size of zeolite in the macropore of silica gel, form partial size 0.02~0.035 in the mesoporous of silica gel
μm zeolite.
Landau etc. described in Chem.Mater (1999,11:2030-2037) it is a kind of by granular size be 10-
The beta-molecular sieve of 15nm is stable at the method in Aluminum sol: being first dispersed in water gel aluminum hydroxide filter cake, pH=is made
9.05 aluminium hydroxide lotion: by the beta-molecular sieve slurries of its pH=12.7 at room temperature according to Al2O3/ molecular sieve=1:1 weight
Than mixing, to pH=11.8, (dust technology is added after described mixing in the preparation of another two batches sample makes the pH for mixing rear slurry to amount
Respectively 11.0 and 10.0)；After stirring 2h, aging is for 24 hours at room temperature；Precipitating is isolated by decantation, and is dried in vacuo at 50 DEG C
It is 70 weight % to water content.Extrusion granulation and in 120 DEG C of dry 5h, then temperature-programmed calcination.The disadvantages of the method are as follows system
The standby time is longer.
CN201310532073.0 provides a kind of preparation method of hydrocracking catalyst containing heteropoly acid, and this method passes through
The relatively large nickel of crystal grain, aluminum precipitation object are prepared using positive addition, cocurrent process prepares the relatively small tungsten of crystal grain, silicon and aluminum precipitation
Object mixes above two sediment, after aging, is impregnated with heteropoly acid solution, then hydrocracking catalyst is made in molding.It should
Method promotes its cooperation to act on by adjusting the distribution of hydrogenation active metals, heteropoly acid and aluminium oxide and amorphous silica-alumina,
Make catalyst service performance with higher.
CN201310495670.0 provides a kind of preparation method of hydrotreating catalyst, including following content: (1) by oxygen
Change the mashing of aluminium dry glue, organic salt is added, be uniformly mixed, is then separated by solid-liquid separation, is dry, obtaining modified aluminas dry glue powder；(2) will
The mashing of modified aluminas dry glue powder, is added to phosphato-molybdic heteropolyacid (H2PMo12O40) in solution, the organic salt and phosphorus molybdenum in solution are miscellaneous
Polyacid is reacted, and after reaction, separation of solid and liquid, drying, extruded moulding, roasting obtain catalyst precursor；(3) it will urge
Agent presoma impregnates coagent metal, dry, and roasting obtains catalyst prod.The catalyst of the method for the present invention preparation, it is living
Property component be evenly distributed in catalytic inner, be easy vulcanization, active metal is high in catalyst surface dispersion degree, improves catalyst
Activity and active metal utilization rate and catalyst life.
CN200910209531.0 provides a kind of composite solid-acid catalyst and preparation method thereof, by 50-80 weight %'s
The heteropolyacid salt of the 15~48wt% of porous inorganic carrier and load thereon and the inorganic acid composition of 2~6wt%.The present invention is also
Provide a kind of method for preparing above-mentioned composite solid-acid catalyst.The acid centre class of composite solid-acid catalyst of the invention
Type is acid, and acid site density is not less than 1.4mol H+/g, and acid strength distribution is uniform, is a kind of solid acid haveing excellent performance
Catalyst.
The preparation method of the micro--mesoporous composite material referred in above-mentioned document or patent either process it is more complicated or
The synthesis technology time is long.CN102000604A introduces microwave processing process during synthesizing Y/MCM-41 composite molecular screen,
Ancillary equipment is increased, the cost for synthesizing composite molecular screen is increased considerably.In addition mentioned in document above or patent it is micro--
Mesoporous part in mesoporous composite material is irregular hole.In the above patent, heteropoly acid generally with the macropores such as aluminium oxide, sial without
Amorphous configuration material load or mixing, but these materials, compared with regular mesoporous material, specific surface area is relatively low, drop
The low catalytic reaction activity of heteropoly acid.Micro porous molecular sieve is since aperture is smaller, and heteropoly acid molecule is relatively large, after load
It is larger that specific surface area and hole hold loss, it is difficult to play catalytic activity.The mesopore molecular sieve developed in recent years is greatly improved point
Sub- sieve ratio surface area, Kong Rong and aperture, but there are thermostabilizations for the mesopore molecular sieves such as mesopore molecular sieve such as SBA-15 and MCM-41
Property it is poor, under long-time high-temperature condition, skeleton structure is easy to collapse, and is easy permanently to lose catalytic activity.
Summary of the invention
The purpose of the present invention is the Y/EU-1/ that the preparation process by improving ASA, first acquisition ASA have rule mesoporous
ZSM-5/ASA composite material, secondly by H3PMo12-X-YWXLaYO40·nH2O heteropoly acid aqueous solution, surfactant and Y/EU-1/
ZSM-5/ASA composite material is mixed with beating, constant temperature aging process, and the Y/EU-1/ZSM-5/ mesoporous with rule is obtained after dry
ASA/ heteropoly acid composite material.
The present invention provides a kind of preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material, includes the following steps:
(1) prepares directed agents:
Sodium hydroxide and silicon source are added to the water, or sodium hydroxide is added to the water to after being completely dissolved and is added again
Enter silicon source, forms sodium aluminate solution A, Al in solution A2O3Content be 2.5~10wt%, Na2O content is 8~35wt%；
Solution A and water glass solution are added sequentially in deionized water under stiring, it is after mixing evenly, static old at 15~50 DEG C
Change 0.5~60h, directed agents are made；The molar ratio of each component is Na in directed agents2O:Al2O3:SiO2:H2O=10~20:1:14
~18:240~440；
(2) reaction mixture of preparation synthesis NaY molecular sieve:
Silicon source is dissolved in water, Al is formed2O3Content is the solution B of 1~4wt%；Sodium hydroxide and silicon source are added to
In water or sodium hydroxide is added to the water to after being completely dissolved and adds silicon source, formation sodium aluminate solution C, in solution C
Al2O3Content be 3~9wt%, Na2O content is 1~20wt%；The directed agents, the solution B and the solution C are added
Enter the reaction mixture that synthesis NaY molecular sieve is made into water glass solution；By the weight of reaction mixture for 100wt% in terms of,
The additional amount of directed agents is 0.5~20wt%, obtains the reaction mixture of synthesis NaY molecular sieve, the molar ratio of each component are as follows:
Na2O:Al2O3:SiO2:H2O=3~10:1:8~18:180~320；
(3) hydrothermal crystallizing synthesizes:
The reaction mixture for the synthesis NaY molecular sieve that step (2) is obtained 8~48h of crystallization at 80~140 DEG C, obtains
NaY molecular sieve slurries；
(4) .EU-1 and the preparation of ZSM-5 molecular sieve slurries:
According to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is 1~5:1~5:1~10, by EU-1 and ZSM-5
Molecular sieve disperses in aqueous solution, to be heated to 70~80 DEG C, and constant temperature stirs 1~10h, obtains EU-1 and ZSM-5 molecular sieve slurries；
The aqueous solution is the aqueous solution of 1~5wt%KOH and 1~5wt% hexamethylene diamine；
(5) preparation of .Y/EU-1/ZSM-5/ASA composite material:
Surfactant is added in the NaY molecular sieve slurries, EU-1 the and ZSM-5 molecule is added while stirring
Screening the pulp liquid adds alkaline silicon source, and the pH value for being adjusted with acid system is 7~9, finally by solid mixture matter obtained above
Be filtered, washed, 100~150 DEG C of dry 4~48h, 400~800 DEG C roasting 2~for 24 hours, it is compound to obtain Y/EU-1/ZSM-5/ASA
Material；
(6) preparation of .Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material:
In H3PMo12-X-YWXLaYO40·nH2Be added surfactant in O heteropoly acid aqueous solution, and with the Y/EU-1/
ZSM-5/ASA composite material is mixed with beating, up to mesoporous Y/EU-1/ after 50~100 DEG C of constant temperature 1~10h of aging process, drying
ZSM-5/ASA/ heteropoly acid composite material；It is 0.001~1, n is 30~50 that wherein X, which is 0.01~11, Y,.
The preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the present invention, wherein Y/EU-1/
ZSM-5/ASA composite material and the heteropoly acid quality usage ratio are preferably 65%~90%:10%~35%.
The preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the present invention, wherein in step (6),
The surfactant is preferably that CTAB, neopelex, lauryl sodium sulfate and polyethylene glycol are one such
Or it is several.
The preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the present invention, wherein in step (5),
The surfactant is preferably one or both of CTAB, P123 and F127.
The preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the present invention, wherein in step (5),
The additional amount of the surfactant preferably accounts for 1~6wt% of Y/EU-1/ZSM-5/ASA composite weight.
The preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the present invention, wherein Y/EU-1/
The content of Y molecular sieve is preferably 10~80wt% in ZSM-5/ASA composite material, and the content of EU-1 molecular sieve is preferably 1~
5wt%, the content of ZSM-5 molecular sieve is preferably 1~5wt%, remaining is sieve and silica-sesquioxide.
The preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the present invention, wherein Y/EU-1/
The SiO of sieve and silica-sesquioxide in ZSM-5/ASA composite material2With Al2O3Molar ratio be preferably 1~10:1.
The present invention also provides a kind of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite materials, are above-mentioned Y/EU-1/ZSM-5/
Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material made from the preparation method of ASA/ heteropoly acid composite material.
The present invention can be also described below:
Surfactant of the present invention mainly has tri- kinds of nonionic surfactants of CTAB, P123 and F127, makes
It can be used that one such or two kinds carry out the preparation of Y/EU-1/ASA composite material the used time.
Mainly there are also CTAB, neopelex, lauryl sodium sulfate, poly- second for surfactant of the present invention
One such or several preparations to carry out Y/ASA/ heteropoly acid composite material can be used in glycol when in use.
Silicon source used in Y/EU-1/ZSM-5/ASA composite material preparation process of the present invention is commonly used in the art
, such as sodium metaaluminate, boehmite, boehmite, aluminum nitrate, aluminum sulfate, aluminium hydroxide and/or gibbsite, alkaline aluminium
Source be it is commonly used in the art, aluminium therein can from sodium metaaluminate or be dissolved in sodium hydroxide solution boehmite,
Boehmite, aluminium hydroxide, gibbsite.Acid is acid generally in the art, preferably inorganic acid, such as sulfuric acid, hydrochloric acid, nitric acid
Deng.
The heat of NaY molecular sieve in the Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material prepared using method of the invention
Stability is maintained, and the differential thermal of Y type molecular sieve destroys in the product Y/EU-1/ASA/ heteropoly acid composite material that this method obtains
Temperature can be greater than 960 DEG C, even up to 1008 DEG C~1100 DEG C；Maximum crystal grain is maintained at 400nm or less.
The present invention also provides one kind by Y/EU-1/ZSM-5/ASA composite material obtained by the above method.
The content of Y molecular sieve is 10~80wt%, the content of EU-1 molecular sieve in Y/EU-1/ZSM-5/ASA composite material
For 1~5wt%, the content of ZSM-5 molecular sieve is 1~5wt%, remaining is sieve and silica-sesquioxide (SiO2/Al2O3) and Al2O3、SiO2
One of, the SiO of sieve and silica-sesquioxide2With Al2O3Molar ratio be preferably 1:1~10:1.
NaY molecular sieve differential thermal fail temperature is reachable in Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the invention
1008 DEG C~1100 DEG C, the mesoporous average pore size of rule is 3~10nm, and total pore volume is 0.46~0.58mL/g, and Micropore volume is
0.20~0.30mL/g, mesoporous 0.24~0.33mL/g of Kong Rongwei.
Heteropoly acid used in Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material of the present invention is high with having
Thermal stability, can be with resistance to 800 DEG C without decomposing.
In conclusion NaY molecular sieve has crystalline substance in Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material produced by the present invention
Grain small (100~400nm), framework si-al ratio are high, thermal stability raising is (higher by 5 than the differential thermal fail temperature of corresponding NaY molecular sieve
DEG C or more) and the mesoporous composition of rule less than the micropore of 1nm and 3~10nm micro--composite mesoporous pore structure the characteristics of.Secondly,
Heteropoly acid used in the present invention has high thermal stability, can be with resistance to 800 DEG C without decomposing.Heteropoly acid and the mesoporous Y/EU- of rule
1/ASA composite material combines, and the mesoporous Y/EU-1/ASA/ heteropoly acid composite material of formation rule effectively improves composite material
Catalytic performance and catalytic activity.As the main active component of wax oil hydrogenation catalyst, it is compound to improve Y/EU-1/ASA/ heteropoly acid
The thermal stability and diffusivity of material play a significant role wax oil hydrogenation reaction.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Analysis test method:
The measurement of the relative crystallinity and framework si-al ratio of NaY molecular sieve: using the production of Bruker company, Germany
D8Advance X-ray diffractometer, determination condition are as follows: CuK α radiation, pipe press 40kV, tube current 40mA.Its measuring method according to
SH/T 0340-92 standard method measurement (see " standard of chemical industry compilation ", China Standards Press publishes for 2000), bone
The measurement of frame silica alumina ratio be by SH/T 0399-92 standard method, (see " standard of chemical industry compilation ", China Standards Press,
2000 publish) measurement and according to the following formula:
Calculate the lattice constant a of NaY molecular sieve.
Then according to Breck-Flanigen formula:
Calculate the framework si-al ratio of NaY molecular sieve.
Sem analysis uses the 435VP type scanning electron microscope of Britain LEO company production, acceleration voltage 20kV, sample
It is gold-plated with physical method before testing.
Thermal stability determination carries out on German Nai Chi instrument company STA 409PC type thermal analyzer.Experiment is in Ar atmosphere
Middle progress, heating rate are 10 DEG C/min, temperature range: room temperature~1200 DEG C.
Specific surface area and hole hold test: the measurement of the specific surface area and pore structure of catalyst and molecular sieve exists
It is carried out in the ASAP2020M specific surface and lacunarity analysis instrument of the production of Micromeritics company, according to BET method calculating ratio table
Area；BJH method calculated pore.
Embodiment 1:
The synthesis of Y/EU-1/ZSM-5/ASA composite material
(1) it the preparation of directed agents: takes 24.7g sodium hydroxide (Beijing Chemical Plant analyzes pure) to be added in 45.9g water, stirs
It mixes to sodium hydroxide and all dissolves, add 6.5g sodium metaaluminate (research institute, Shandong Aluminium Industrial Corp, industrial goods, Al2O3Content
49.1wt%), stirring is all dissolved to sodium metaaluminate, obtains sodium aluminate solution A.By 70g solution A and 100g waterglass (Beijing
Red Star water glass plant, SiO2Content 27.81wt%, Na2O content 8.74wt%) it successively pours into 65.5g deionized water, stirring is equal
After even at 30 DEG C static ageing 22h, obtain directed agents.The molar ratio of directed agents each component are as follows: 16Na2O:Al2O3:16SiO2:
330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (the same step of specification
1), stirring forms sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B and solution C according to conventional NaY molecule
Sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g water again after mixing evenly, synthesis is made in step 1)
The reaction mixture of NaY molecular sieve.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；By reaction mixture
It goes in autoclave, the crystallization 22h at 105 DEG C.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries, i.e.,
Obtain NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 4wt%KOH and 4wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 0.8g sodium hydroxide is dissolved in 6.2g water, is added
1g sodium metaaluminate, stirring to sodium metaaluminate are all dissolved, and solution D is obtained.The NaY type molecular sieve and mother liquor that step (2) is obtained are cold
But it to room temperature, is transferred in beaker, static layering, upper layer mother liquor 32mL is taken out, then to the mixing of NaY type molecular sieve and mother liquor
Surfactant P123 0.8g is added in suspended matter and stirs 30min at 20 DEG C, solution D and EU-1 and ZSM-5 are added later
Molecular sieve pulp E continues to stir 1h after adding, sulfuric acid is added in the mixture of above-mentioned stirring, the pH value of regulation system is
7.Finally solid matter obtained above is filtered, washed, 120 DEG C of dry 12h, 500 DEG C of roasting 4h, obtains Y/EU-1/ZSM-
5/ASA composite material, intermediary hole part are sieve and silica-sesquioxide, and the molar ratio of sieve and silica-sesquioxide is 8.5:1, mesoporous to be situated between for rule
Hole, aperture 5nm, the content of Y molecular sieve are 62wt%.The differential thermal of NaY molecular sieve in Y/EU-1/ZSM-5/ASA composite material
Fail temperature is 1010 DEG C, and texture property is shown in Table 1.
Embodiment 2
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 75g waterglass, adds 48.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 6.2Na2O:Al2O3:12SiO2:260H2O；Reaction mixture is gone in autoclave, the crystallization at 105 DEG C
22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 5wt%KOH and 5wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 7.5g sodium hydroxide is dissolved in 58g water, is added
9.2g sodium metaaluminate, stirring to sodium metaaluminate are all dissolved, and solution D is obtained.The Y type molecular sieve and mother liquor that step (2) is obtained are cold
But to room temperature, be transferred in beaker, at 25 DEG C, sequentially add P123 1.6g while stirring, waterglass 7.8g and solution D and
EU-1 and ZSM-5 molecular sieve slurries E.Continue to stir 2h at 25 DEG C, nitric acid solution is added in the mixture of above-mentioned stirring,
Finally make the pH value 8.5 of system.Finally solid matter obtained above is filtered, washed, 150 DEG C of dry 4h, 450 DEG C of roastings
10h, obtains Y/EU-1/ZSM-5/ASA composite material, and intermediary hole part is sieve and silica-sesquioxide, the molar ratio of sieve and silica-sesquioxide
For 5:1, mesoporous is mesoporous, the aperture 8nm of rule, and the content of Y molecular sieve is 35wt%.Y/EU-1/ZSM-5/ASA composite material
The differential thermal fail temperature of middle NaY molecular sieve is 1008 DEG C, and texture property is shown in Table 1.
Embodiment 3
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 32.1g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 113g
Waterglass successively pours into 79g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents each group
The molar ratio divided are as follows: 20Na2O:Al2O3:18SiO2:440H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 162g waterglass, adds 48.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 10Na2O:Al2O3:18SiO2:320H2O；Reaction mixture is gone in autoclave, the crystallization 22h at 105 DEG C.
Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 3wt%KOH and 3wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water, then plus
Enter 16.1g sodium metaaluminate, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y type molecular sieve and mother liquor that step (2) is obtained
It is cooled to room temperature, taking-up mother liquor 90mL, in the beaker for being then transferred to the mixture of remaining mother liquor and Y type molecular sieve, In
CTAB6.5g is added while stirring at 18 DEG C, then proceedes to that EU-1 and ZSM-5 molecular sieve slurries E and solution D is added, adds solution
Continue to stir 4h at 18 DEG C after D, hydrochloric acid solution is added in the mixture of above-mentioned stirring, the pH value of regulation system is 7.8.Most
Solid matter obtained above is filtered, washed afterwards, 110 DEG C of dry 32h, 600 DEG C of roasting 5h, obtains Y/EU-1/ZSM-5/ASA
Composite material, intermediary hole part are sieve and silica-sesquioxide, and the molar ratio of sieve and silica-sesquioxide is 4.5:1, mesoporous for regular mesoporous, hole
Diameter is 5.5nm, and the content of Y type molecular sieve is 62wt%.The differential thermal of NaY molecular sieve is broken in Y/EU-1/ZSM-5/ASA composite material
Bad temperature is 1020 DEG C, and texture property is shown in Table 1.
Embodiment 4
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 75g waterglass, adds 48.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 6.2Na2O:Al2O3:12SiO2:260H2O；Reaction mixture is gone in autoclave, the crystallization at 105 DEG C
22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 3wt%KOH and 3wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 37.6mL water, then plus
Enter 4.4g aluminium hydroxide, stirring to aluminium hydroxide is all dissolved, and solution D is obtained.The NaY molecule containing mother liquor that step (2) is obtained
It is 9 that sieve, which is filtered, washed to the pH value of washing water, then adds water to be beaten in NaY type molecular sieve, is added while stirring at 20 DEG C
CTAB 4.8g stirs 30min, and EU-1 and ZSM-5 molecular sieve slurries E, solution D and sulfuric acid, the pH value of regulation system is then added
It is 8.0.Finally mixture obtained above is filtered, washed, 125 DEG C of dry 16h, 600 DEG C of roasting 3h obtain Y/EU-1/
ZSM-5/ASA composite material.Its intermediary hole part is sieve and silica-sesquioxide, and the molar ratio of sieve and silica-sesquioxide is 5.5:1, mesoporous for rule
Then mesoporous, aperture 3.5nm, the content of Y type molecular sieve is 60wt%.NaY molecule in Y/EU-1/ZSM-5/ASA composite material
1105 DEG C of the differential thermal fail temperature of sieve, texture property is shown in Table 1.
Embodiment 5
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 75g waterglass, adds 48.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 6.2Na2O:Al2O3:12SiO2:260H2O；Reaction mixture is gone in autoclave, the crystallization at 105 DEG C
22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 3wt%KOH and 3wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 99.6g waterglass is poured into 171.4mL water, solution is obtained
D.The pH value that the NaY molecular sieve containing mother liquor that step (2) obtains is filtered, washed to washing water is 9, then by NaY type molecule
Sieve plus water mashing, are added F1273.8g and EU-1 and ZSM-5 molecular sieve slurries E and solution D, later while stirring at 20 DEG C
It is 8.0 with the pH value of sulfuric acid regulation system.Finally compounding substances obtained above are filtered, washed, 120 DEG C of dry 10h, 550
DEG C roasting 5h, obtains Y/EU-1/ZSM-5/ASA composite material, the molar ratio of sieve and silica-sesquioxide is 4.5:1, mesoporous to be situated between for rule
Hole, aperture 6.5nm, the content of Y type molecular sieve are 65wt%.NaY molecular sieve in Y/EU-1/ZSM-5/ASA composite material
1008 DEG C of differential thermal fail temperature, texture property is shown in Table 1.
Embodiment 6
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 75g waterglass, adds 48.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 6.2Na2O:Al2O3:12SiO2:260H2O；Reaction mixture is gone in autoclave, the crystallization at 105 DEG C
22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 2wt%KOH and 2wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water, then plus
Enter 4.4g sodium metaaluminate, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y type molecular sieve and mother liquor that step (2) is obtained
It is cooled to room temperature, takes out mother liquor 180mL, then the mixture of remaining mother liquor and Y type molecular sieve is transferred in plastic beaker,
Sequentially add P123 1.3g, EU-1 and ZSM-5 molecular sieve slurries E, solution D and sulfuric acid, regulation system while stirring at 30 DEG C
PH value be 7.5.Finally solid mixture matter obtained above is filtered, washed, 130 DEG C of dry 8h, 650 DEG C of roasting 4h, is obtained
To Y/EU-1/ZSM-5/ASA composite material, intermediary hole part is sieve and silica-sesquioxide, and the silica alumina ratio of sieve and silica-sesquioxide is
2.5:1, mesoporous is mesoporous, the aperture 9.5nm of rule, on the basis of Y/EU-1/ZSM-5/ASA composite material, Y type molecular sieve
Content is 80wt%.1055 DEG C of the differential thermal fail temperature of NaY molecular sieve, texture property in Y/EU-1/ZSM-5/ASA composite material
It is shown in Table 1.
Embodiment 7
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 75g waterglass, adds 48.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 6.2Na2O:Al2O3:12SiO2:260H2O；Reaction mixture is gone in autoclave, the crystallization at 105 DEG C
22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 1wt%KOH and 5wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water, then plus
Enter 8.8g sodium metaaluminate, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y type molecular sieve and mother liquor that step (2) is obtained
It is cooled to room temperature, takes out mother liquor 200mL, then the mixture of remaining mother liquor and Y type molecular sieve is transferred in beaker, 25
P123 0.8g and F127 4.2g is added at DEG C while stirring after mixing evenly, sequentially adds EU-1 and ZSM-5 molecular sieve is starched
Liquid E, solution D and sulfuric acid, the pH value of regulation system are 8.0.Finally solid matter obtained above is filtered, washed, 120 DEG C it is dry
Dry 12h, 550 DEG C of roasting 4h, obtain Y/EU-1/ZSM-5/ASA composite material, and intermediary hole part is sieve and silica-sesquioxide, sial
The silica alumina ratio of oxide is 1.5:1, and mesoporous is mesoporous, the aperture 9.2nm of rule, with Y/EU-1/ZSM-5/ASA composite wood
On the basis of material, the content of Y type molecular sieve is 80wt%.The differential thermal of NaY molecular sieve is broken in Y/EU-1/ZSM-5/ASA composite material
1027 DEG C of bad temperature, texture property is shown in Table 1.
Embodiment 8
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 12.8g sodium hydroxide to be added in 35.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 88g
Waterglass successively pours into 65.5g deionized water, and the static ageing 30h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 10Na2O:Al2O3:14SiO2:240H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 30.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 30.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 55g waterglass, adds 28.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 6Na2O:Al2O3:8SiO2:180H2O；Reaction mixture is gone in autoclave, the crystallization 48h at 105 DEG C.Water
Thermal crystallisation finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 5wt%KOH and 1wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water, then plus
Enter 8.8g sodium metaaluminate, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y type molecular sieve and mother liquor that step (2) is obtained
It is cooled to room temperature, takes out mother liquor 220mL, then the mixture of remaining mother liquor and Y type molecular sieve is transferred in beaker, 25
P1231.2g and CTAB 3.8g is added at DEG C while stirring, after mixing evenly, sequentially adds EU-1 and ZSM-5 molecular sieve is starched
Liquid E, solution D and sulfuric acid, the pH value of regulation system are 8.0.Finally solid matter obtained above is filtered, washed, 120 DEG C it is dry
Dry 8h, 600 DEG C of roasting 4h, obtain Y/EU-1/ZSM-5/ASA composite material, and intermediary hole part is sieve and silica-sesquioxide, sial oxygen
The silica alumina ratio of compound is 1:1, and mesoporous is mesoporous, the aperture 7.5nm of rule, and the content of Y type molecular sieve is 80wt%.Y/
1034 DEG C of the differential thermal fail temperature of NaY molecular sieve in EU-1/ZSM-5/ASA composite material, texture property is shown in Table 1.
Embodiment 9
Except special instruction, each raw material sources are the same as embodiment 1.
(1) preparation of directed agents: taking 24.7g sodium hydroxide to be added in 45.9g water, stirs all molten to sodium hydroxide
Solution adds 6.5g sodium metaaluminate, and stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution A.By 70g solution A and 100g
Waterglass successively pours into 65.5g deionized water, and the static ageing 22h at 30 DEG C, obtains directed agents after mixing evenly.Directed agents are each
The molar ratio of component are as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate, stirring to completely it is molten
Solution forms sodium aluminate solution C.Successively according to conventional NaY molecular sieve preparation step by 10.3g directed agents, solution B and solution C
It is added in 75g waterglass, adds 48.5g water again after mixing evenly, the reaction mixture of synthesis NaY molecular sieve is made.Each component
Molar ratio be 6.2Na2O:Al2O3:12SiO2:260H2O；Reaction mixture is gone in autoclave, the crystallization at 105 DEG C
22h.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries to get NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 3wt%KOH and 3wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water, then plus
Enter 8.8g sodium metaaluminate, stirring to sodium metaaluminate is all dissolved, and solution D is obtained.The Y type molecular sieve and mother liquor that step (2) is obtained
It is cooled to room temperature, takes out mother liquor 200mL, then the mixture of remaining mother liquor and Y type molecular sieve is transferred in plastic beaker,
CTAB 4.2g and F127 8.2g is added while stirring at 25 DEG C, sequentially adds EU-1 and ZSM-5 molecular sieve slurries E, solution D
And sulfuric acid, the pH value of regulation system are 8.0.Finally solid matter obtained above is filtered, washed, 120 DEG C of dry 12h, 550
DEG C roasting 4h, obtains Y/EU-1/ASA composite material, intermediary hole part is sieve and silica-sesquioxide, the sial mole of sieve and silica-sesquioxide
Than for 1.5:1, mesoporous is mesoporous, the aperture 7.3nm of rule, and the content of Y type molecular sieve is 70wt%.Y/EU-1/ZSM-5/ASA
1050 DEG C of the differential thermal fail temperature of NaY molecular sieve in composite material, texture property is shown in Table 1.
Comparative example 1
P123 is not added using the condition of embodiment 1, but when preparing Y/ASA composite material.
(1) it the preparation of directed agents: takes 24.7g sodium hydroxide (Beijing Chemical Plant analyzes pure) to be added in 45.9g water, stirs
It mixes to sodium hydroxide and all dissolves, add 6.5g sodium metaaluminate (research institute, Shandong Aluminium Industrial Corp, industrial goods, Al2O3Content
49.1wt%), stirring is all dissolved to sodium metaaluminate, obtains sodium aluminate solution A.By 70g solution A and 100g waterglass (Beijing
Red Star water glass plant, SiO2Content 27.81wt%, Na2O content 8.74wt%) it successively pours into 65.5g deionized water, stirring is equal
After even at 30 DEG C static ageing 22h, obtain directed agents.The molar ratio of directed agents each component are as follows: 16Na2O:Al2O3:16SiO2:
330H2O。
(2) preparation of NaY type molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3Content is
The aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (the same step of specification
1), stirring forms sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B and solution C according to conventional NaY molecule
Sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g water again after mixing evenly, synthesis is made in step 1)
The reaction mixture of NaY molecular sieve.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；By reaction mixture
It goes in autoclave, the crystallization 22h at 105 DEG C.Hydrothermal crystallizing finishes, and takes out molecular sieve and mother liquor, is filtered, washed, dries, i.e.,
Obtain NaY type zeolite product.
The relative crystallinity of gained NaY molecular sieve is 95%, framework si-al ratio 5.2, partial size 200nm, and differential thermal destroys
Temperature is 950 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 4wt%KOH and 4wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: in addition to surfactant is not added, the step of with embodiment 1
(4).Mesoporous aperture is 3.3~5.2nm.The differential thermal fail temperature of NaY molecular sieve in Y/EU-1/ZSM-5/ASA composite material
910 DEG C, texture property is shown in Table 1.
Comparative example 2
Small crystal grain NaY molecular sieve is prepared by the method for the embodiment 1 of CN 1033503C and prepares Y/ASA composite material.
(1) preparation of directed agents: taking 29.5g sodium hydroxide to be added in 75g water, and stirring to sodium hydroxide is all dissolved,
4.78g boehmite is added, stirring to boehmite is all dissolved, and sodium metaaluminate is obtained.200g waterglass is added to
1h is mixed in the sodium metaaluminate and 12g deionized water of above-mentioned preparation at 35 DEG C, is then made and rubs in 35 DEG C of static aging 6h
You are than being 16Na2O:Al2O3:15SiO2:320H2O, the conventional directed agents of light transmittance < 30%.
189g specification waterglass same as described above is added in conventional directed agents, after placing 1.5h at 30 DEG C, is made
Light transmittance is 90%, and mole group becomes 20.6Na2O:Al2O3:30SiO2:495H2O as clear as crystal improvement directing agent solution, In
It is placed at room temperature for and uses afterwards for 24 hours.
(2) preparation of NaY type molecular sieve: according to molar ratio 3.84Na2O:Al2O3:12SiO2:220H2The synthesizing formula of O,
By 250g specification waterglass same as described above, the improvement directed agents of the above-mentioned preparation of 510g, 160g Al2O3Content is 6.8wt%
Aluminum sulfate solution and 9.7g sodium aluminate solution (Al2O3Content 7.5wt%, Na2O content is 15wt%) 1h is mixed, so
After be warming up to 97 DEG C, crystallization 26h, it is filtering, dry.
The relative crystallinity of gained NaY molecular sieve is 79%, framework si-al ratio 5.8, partial size 100nm, and differential thermal destroys
Temperature is 935 DEG C.
(3) EU-1 and the preparation of ZSM-5 molecular sieve slurries: according to EU-1 molecular sieve: ZSM-5 molecular sieve: water-soluble liquid proportional is
The ZSM-5 molecular sieve of the EU-1 molecular sieve of 2g and 2g is dispersed in the water-soluble of the 4wt%KOH and 4wt% hexamethylene diamine of 10g by 1:1:5
In liquid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains EU-1 and ZSM-5 molecular sieve slurries E.
(4) preparation of Y/EU-1/ZSM-5/ASA composite material: with (4) the step of embodiment 4, CTAB is not added.It is mesoporous
Part is sieve and silica-sesquioxide, and silica alumina ratio 5.5:1, mesoporous aperture is 3.2~6.5nm, Y/EU-1/ZSM-5/ASA composite wood
980 DEG C of the differential thermal fail temperature of NaY molecular sieve in material, texture property is shown in Table 1.
Comparative example 3
By the method synthesis NaY molecular sieve that CN 201010514225.0 is provided and prepare Y/ASA composite material.
(1) synthesize directed agents: take 48g waterglass (modulus 3.0), add 8g polyethylene glycol PEG-2000, at 15 DEG C with
200 revs/min of mixing speed stirs 1h, obtains solution A；7.8g sodium hydroxide is dissolved in 24mL water, meta-aluminic acid is added
Sodium 1.6g, stirring to sodium metaaluminate are all dissolved, and solution B is obtained；Solution A is stirred under 3000 revs/min of mixing speed, it will
Solution B is poured into solution A, and 1.5h is stirred in continuation under 3000 revs/min of mixing speeds, finally with 200 revs/min at 15 DEG C
Mixing speed stirs aging 12h, and 20.4mL water is supplemented after aging, continues to stir at 15 DEG C with 200 revs/min of mixing speeds
0.5h.In addition to PEG-2000, the molar ratio of remaining each component is 18Na2O:Al2O3:22SiO2:426H2O.It is spare to place 10h.
(2) it synthesizes NaY type molecular sieve: 3g sodium hydroxide being dissolved in 23.3mL water, 3.7g sodium metaaluminate is added, stirs
It mixes to sodium metaaluminate and all dissolves, 10.5g polyethylene glycol 2000 (PEG-2000) is added under stiring to whole dissolutions, obtains solution
C；15g aluminum sulfate is dissolved in 25mL water, solution D is obtained.C solution is stirred with 3000 revs/min of mixing speed, is sequentially added
Water glass solution 90g, directed agents 10.6g, solution D and solution C, obtain colloidal sol E.Colloidal sol E is stirred at 15 DEG C with 3000 revs/min
It mixes speed to stir 20 minutes, then stirs 1h with 200 revs/min of mixing speeds, obtain colorless gel.Obtained colorless gel is turned
It moves on in the synthesis reactor of inner liner polytetrafluoroethylene, the hydrothermal crystallizing 32h at 104 DEG C obtains NaY type molecular sieve.
The relative crystallinity of gained nano NaY molecular sieve is 82%, framework si-al ratio 5.0, partial size are 20~100nm,
Differential thermal fail temperature is 900 DEG C.
(3) preparation of Y/ASA composite material: with (4) the step of embodiment 2, P123 is not added.Mesoporous part is sial oxygen
Compound, silica alumina ratio 5:1, mesoporous aperture are 6.2~8.2nm, and the differential thermal of NaY molecular sieve is broken in Y/EU-1/ASA composite material
985 DEG C of bad temperature, texture property is shown in Table 1.
The texture property of NaY in 1 Y/EU-1/ZSM-5/ASA composite material of table
In Y/EU-1/ZSM-5/ASA composite material it can be seen from the result of table 1 using method preparation of the invention
The differential thermal fail temperature of NaY molecular sieve be improved.Y/EU-1/ZSM-5/ASA composite material tool prepared by the present invention
There are biggish total pore volume and mesoporous Kong Rong, mesoporous average pore size is 3~10nm and is regular meso-hole structure, is organic macromolecule
Conversion provides open space, is conducive to the Efficient Conversion of heavy oil molecules.And in composite material preparation process, it is not added with table
The random distribution of mesoporous pore size of face activity and the composite material of preparation.
Embodiment 10
Prepared Y/EU-1/ZSM-5/ASA composite material 10g in Example 1, by the H of 2g3PMo12-X- YWXLaYO40·nH2O heteropoly acid is dissolved in 8g water, then CTAB is added in above-mentioned solution, after mixing evenly again by Y/EU-1/
ZSM-5/ASA composite material is added in solution, dry to get Y/EU-1/ZSM- in 120 DEG C in 70 DEG C of constant temperature aging process 2h
5/ASA/ heteropoly acid composite material.Product property such as table 2 is measured after 300 DEG C of roasting 4h.
Embodiment 11
Prepared Y/EU-1/ZSM-5/ASA composite material 10g in Example 2, by the H of 3g3PMo12-X- YWXLaYO40·nH2O heteropoly acid is dissolved in 8g water, then neopelex is added in above-mentioned solution, after mixing evenly
Y/EU-1/ZSM-5/ASA composite material is added in solution again, in 80 DEG C of constant temperature aging process 4h, in 120 DEG C it is dry to get
Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material.Product property such as table 2 is measured after 400 DEG C of roasting 2h.
Embodiment 12
Prepared Y/EU-1/ZSM-5/ASA composite material 10g in Example 7, by the H of 4g3PMo12-X- YWXLaYO40·nH2O heteropoly acid is dissolved in 8g water, then neopelex is added in above-mentioned solution, after mixing evenly
Y/EU-1/ZSM-5/ASA composite material is added in solution again, in 90 DEG C of constant temperature aging process 6h, in 100 DEG C it is dry to get
Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material.Product property such as table 2 is measured after 500 DEG C of roasting 2h.
2 Y/ASA/ heteropoly acid composite properties of table
Claims (7)
1. a kind of preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material, includes the following steps:
(1) prepares directed agents:
Sodium hydroxide and silicon source are added to the water, or sodium hydroxide is added to the water to after being completely dissolved and adds aluminium
Source forms sodium aluminate solution A, Al in solution A2O3Content be 2.5~10wt%, Na2O content is 8~35wt%；It is stirring
It is lower that solution A and water glass solution are added sequentially in deionized water, after mixing evenly, the static ageing 0.5 at 15~50 DEG C
Directed agents are made in~60h；The molar ratio of each component is Na in directed agents2O:Al2O3:SiO2: H2O=10~20:1:14~18:240
~440；
(2) reaction mixture of preparation synthesis NaY molecular sieve:
Silicon source is dissolved in water, Al is formed2O3Content is the solution B of 1~4wt%；Sodium hydroxide and silicon source are added to the water,
Or sodium hydroxide is added to the water to after being completely dissolved and adds silicon source, forms sodium aluminate solution C, Al in solution C2O3's
Content is 3~9 wt%, Na2O content is 1~20wt%；The directed agents, the solution B and the solution C are added to water glass
The reaction mixture of synthesis NaY molecular sieve is made in glass solution；By the weight of reaction mixture for 100wt% in terms of, directed agents plus
Entering amount is 0.5 ~ 20 wt%, obtains the reaction mixture of synthesis NaY molecular sieve, the molar ratio of each component are as follows: Na2O :
Al2O3 : SiO2 :H2O=3~10:1:8~18:180~320；
(3) hydrothermal crystallizing synthesizes:
The reaction mixture for the synthesis NaY molecular sieve that step (2) is obtained 8~48h of crystallization at 80~140 DEG C obtains NaY points
Sub- screening the pulp liquid；
(4) EU-1 and the preparation of ZSM-5 molecular sieve slurries:
According to EU-1 molecular sieve: ZSM-5 molecular sieve: the mass ratio of aqueous solution is 1 ~ 5:1 ~ 5:1 ~ 10, by EU-1 and ZSM-5 molecule
Screening dissipates in aqueous solution, is heated to 70 ~ 80 DEG C, and constant temperature stirs 1 ~ 10h, obtains EU-1 and ZSM-5 molecular sieve slurries；The water
Solution is the aqueous solution of 1 ~ 5wt%KOH and 1 ~ 5wt% hexamethylene diamine；
(5) preparation of Y/EU-1/ZSM-5/ASA composite material:
Surfactant is added in the NaY molecular sieve slurries, the EU-1 and ZSM-5 molecular sieve slurry are added while stirring
Liquid adds alkaline silicon source, and the pH value for being adjusted with acid system is 7~9, finally by solid mixture matter mistake obtained above
Filter, washing, 100~150 DEG C of 4~48 h of drying, 400~800 DEG C of 2~24 h of roasting, it is compound to obtain Y/EU-1/ZSM-5/ASA
Material, wherein ASA is the amorphous silica-alumina of synthesis；Wherein the surfactant be one of CTAB, P123 and F127 or
Two kinds；
(6) preparation of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material:
In H3PMo12-X-YWXLaYO40·nH2Be added surfactant in O heteropoly acid aqueous solution, and with the Y/EU-1/ZSM-5/
ASA composite material is mixed with beating, up to mesoporous Y/EU-1/ZSM-5/ after 50 ~ 100 DEG C of constant temperature 1 ~ 10h of aging process, drying
ASA/ heteropoly acid composite material；It is 0.001 ~ 1, n is 30 ~ 50 that wherein X, which is 0.01 ~ 11, Y,.
2. the preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material according to claim 1, feature exist
In Y/EU-1/ZSM-5/ASA composite material and the heteropoly acid quality usage ratio are 65% ~ 90%:10% ~ 35%.
3. the preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material according to claim 1, feature exist
In, in step (6), the surfactant be CTAB, neopelex, lauryl sodium sulfate and polyethylene glycol its
One or more of.
4. the preparation method of described in any item Y/EU-1/ZSM-5/ASA/ heteropoly acid composite materials according to claim 1 ~ 3,
It is characterized in that, in step (5), the additional amount of the surfactant accounts for the 1~6 of Y/EU-1/ZSM-5/ASA composite weight
wt %。
5. the preparation method of described in any item Y/EU-1/ZSM-5/ASA/ heteropoly acid composite materials according to claim 1 ~ 3,
It is characterized in that, the content of Y molecular sieve is 10~80 wt%, the content of EU-1 molecular sieve in Y/EU-1/ZSM-5/ASA composite material
Content for 1~5 wt%, ZSM-5 molecular sieve is 1~5 wt%, remaining is sieve and silica-sesquioxide.
6. the preparation method of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material according to claim 5, feature exist
In the SiO of sieve and silica-sesquioxide in Y/EU-1/ZSM-5/ASA composite material2With Al2O3Molar ratio be 1~10:1.
7. a kind of Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material is any one of claim 1 ~ 6 Y/EU-1/
Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material made from the preparation method of ZSM-5/ASA/ heteropoly acid composite material.
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