CN109205636A - The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material - Google Patents
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material Download PDFInfo
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- CN109205636A CN109205636A CN201710519563.5A CN201710519563A CN109205636A CN 109205636 A CN109205636 A CN 109205636A CN 201710519563 A CN201710519563 A CN 201710519563A CN 109205636 A CN109205636 A CN 109205636A
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- zsm
- sapo
- molecular sieve
- solution
- asa
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- 238000002360 preparation method Methods 0.000 title claims abstract description 94
- 239000011799 hole material Substances 0.000 title claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 claims abstract description 228
- 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 227
- 239000002131 composite material Substances 0.000 claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010703 silicon Substances 0.000 claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 168
- 239000000243 solution Substances 0.000 claims description 147
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 97
- 238000003756 stirring Methods 0.000 claims description 83
- 229910001868 water Inorganic materials 0.000 claims description 83
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 59
- 239000011734 sodium Substances 0.000 claims description 59
- 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 claims description 57
- 229910052708 sodium Inorganic materials 0.000 claims description 57
- 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 40
- 235000019353 potassium silicate Nutrition 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 34
- 239000011541 reaction mixture Substances 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 28
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 27
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 238000003786 synthesis reaction Methods 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 230000003068 static effect Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- 229910001593 boehmite Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- 239000002253 acid Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910001679 gibbsite Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 31
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 3
- 239000012452 mother liquor Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 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
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 239000013055 pulp slurry Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- MVEOHWRUBFWKJY-UHFFFAOYSA-N 7-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(O)=CC=C21 MVEOHWRUBFWKJY-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000011160 research Methods 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
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 Y type Chemical compound 0.000 description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical group [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000001788 irregular Effects 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
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000004575 stone Substances 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
- 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
- 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
- 238000004523 catalytic cracking Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 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
- 239000011521 glass Substances 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 208000017262 paroxysmal cold hemoglobinuria Diseases 0.000 description 1
- 239000002245 particle Substances 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
- 238000001556 precipitation Methods 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
- 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/643—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/365—Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
-
- 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
Abstract
The present invention provides a kind of Y/SAPO-34/ZSM-11/ASA multilevel hole material preparation methods, it is characterized in that this method comprises: first synthesizing directed agents, Y/SAPO-34/ZSM-11 composite molecular screen is synthesized using hydrothermal crystallization method, then surfactant, alkaline silicon source and/or alkaline silicon source solution are added in the slurries of Y/SAPO-34/ZSM-11 molecular sieve, product is washed, dry, roasting is to get mesoporous Y/SAPO-34/ZSM-11/ASA multilevel hole material.
Description
Technical field
The present invention provides a kind of Y/SAPO-34/ZSM-11/ASA multilevel hole material preparation method, first synthesis directed agents,
Y/SAPO-34/ZSM-11 composite molecular screen is synthesized using hydrothermal crystallization method, then in the slurry of Y/SAPO-34/ZSM-11 molecular sieve
Be added surfactant, alkaline silicon source and/or alkaline silicon source solution in liquid, product is washed, it is dry, roast to get mesoporous Y/
SAPO-34/ZSM-11/ASA 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.
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 12~70h of crystallization at 80-180 DEG C, is filtered, is washed, and hud typed composite material is obtained.Y molecular sieve is in composite wood
Content in material is in 10~30wt%, and the partial size of composite material is at 2~10 μm.Y type molecular sieve is not involved in titanium dioxide in this method
The outgrowth of silicon, without chemical bond between Y type molecular sieve and silica, silica cannot provide acidity, various
It can only play the role of selecting type in catalysis reaction, so the acidity of composite material can only be realized by modulation Y molecular sieve.But it is mesoporous to be
Irregular multi-stage porous.
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 the Y molecular sieve seed-solution containing 27wt%SiO2 and 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, and average pore size is 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.
Prndau 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.
Prndau 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.
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 developing a kind of Y/SAPO-34/ZSM-11/ASA multilevel hole material, directed agents are synthesized first,
Y/SAPO-34/ZSM-11 composite molecular screen is synthesized using hydrothermal crystallization method, then in the slurry of Y/SAPO-34/ZSM-11 molecular sieve
Be added surfactant, alkaline silicon source and/or alkaline silicon source solution in liquid, product is washed, it is dry, roast to get mesoporous Y/
SAPO-34/ZSM-11/ASA composite material.
The present invention provides a kind of preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material, includes the following steps:
(1) directed agents are prepared:
Sodium hydroxide and silicon source are added to the water, or aluminium 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=15~17:1:15
~17:250~350；
(2) preparation of slurries D:
According to SAPO-34 molecular sieve: ZSM-11 molecular sieve: aqueous solution mass ratio is 1:0.2~5:3~7, by SAPO-
34 and ZSM-11 molecular sieve disperses in aqueous solution, to be heated to 70~80 DEG C, and constant temperature stirs 2~5h, obtains SAPO-34 and ZSM-
11 molecular sieve pulps adjust the pH value of SAPO-34 and ZSM-11 molecular sieve pulp, obtain SAPO-34 and ZSM-11 molecule screening the pulp
Liquid D；
The aqueous solution is the aqueous solution of 1~10wt% potassium hydroxide and 1~5wt% boric acid；
(3) preparation of Y/SAPO-34/ZSM-11 composite molecular screen slurries E:
Silicon source is dissolved in water, Al is formed2O3Content is the solution B of 1~4wt%；
Sodium hydroxide is added to the water with silicon source or aluminium hydroxide is added to the water to after being completely dissolved and adds aluminium
Source forms sodium aluminate solution C, Al in solution C2O3Content be 3~9wt%, Na2O content is 1~20wt%；
The directed agents, solution B, solution C and slurries D are added to, synthesis NaY molecular sieve is made in water glass solution
Reaction mixture；By the weight of reaction mixture for 100wt% in terms of, the additional amounts of directed agents is 0.5~20wt%, is synthesized
The molar ratio of the reaction mixture each component of NaY are as follows: Na2O:Al2O3:SiO2:H2O=4~8:1:10~15:200~300；
After reaction mixture crystallization, Y/SAPO-34/ZSM-11 composite molecular screen slurries E is obtained；
(4) preparation of Y/SAPO-34/ZSM-11/ASA multilevel hole material
Surfactant is added in the Y/SAPO-34/ZSM-11 composite molecular screen slurries E, alkaline silicon source is added
Or alkaline silicon source solution, and it is adjusted with acid the pH value of system, finally obtained solid mixture matter is filtered, washed, dry, is roasted
It burns, obtains Y/SAPO-34/ZSM-11/ASA multilevel hole material.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: in step (4),
The surfactant is preferably at least one of CTAB, P123 and F127.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: in step (4),
The additional amount of the surfactant is preferably the 1~3wt% for accounting for Y/SAPO-34/ZSM-11/ASA multilevel hole material weight.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: in step (2),
The pH value is preferably 7~8.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: in step (4),
The pH value is preferably 7~9.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: in step (3),
The condition of crystallization is preferred are as follows: 8~48h of crystallization at 80~140 DEG C.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: step (1) with
(3) in, source of aluminium is preferably sodium metaaluminate, boehmite, boehmite, aluminum nitrate, aluminum sulfate, aluminium hydroxide and three water
One or more of aluminium stone.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: in step (4),
The alkalinity silicon source is preferably sodium metaaluminate, or the boehmite, boehmite, the hydroxide that are dissolved in sodium hydroxide solution
Aluminium or gibbsite.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: in step (4),
The acid is preferably sulfuric acid, hydrochloric acid or nitric acid.
The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material of the present invention, in which: the Y/SAPO-
Mesoporous mesoporous for rule in 34/ZSM-11/ASA multilevel hole material, total pore volume is 0.52~0.62mL/g, and Micropore volume is
0.20~0.30mL/g, mesoporous 0.27~0.40mL/g of Kong Rongwei.
The present invention can be with details are as follows:
A kind of Y/SAPO-34/ZSM-11/ASA multilevel hole material preparation method, voluminous heavy naphtha and kerosene hydrogenation cracking
Catalyst preparation includes the following steps:
1, directed agents are prepared: sodium hydroxide and silicon source are added to the water, or sodium hydroxide are added to the water molten
Silicon source is added after solution, forms sodium aluminate solution A, Al in solution A2O3Content be 3.8wt%, Na2O content is 20wt%；
Solution A is added in water glass solution under stiring, after mixing evenly, directed agents are made in the static ageing 3h at 30 DEG C；It leads
Into agent, the molar ratio of each component is 16Na2O:Al2O3:16SiO2:330H2O。
2, prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: aqueous solution
Ratio is 1:1:5, SAPO-34 and ZSM-11 molecular sieve is dispersed in 1~10wt% potassium hydroxide and 1~5wt% boric acid, is added
For heat to 70~80 DEG C, constant temperature stirs 2h, obtains SAPO-34 and ZSM-11 molecular sieve pulp, pH value is adjusted to 7~8, is obtained
SAPO-34 and ZSM-11 molecular sieve pulp D.
3, the preparation of Y/SAPO-34/ZSM-11/ASA: water-soluble silicon source is dissolved in water, and forms Al2O3Content is
The solution B of 2wt%；Sodium hydroxide is added to the water with silicon source or sodium hydroxide is added to the water after dissolution and adds aluminium
Source forms sodium aluminate solution C, Al in solution C2O3Content be 6.5wt%, Na2O content is 13.2wt%；By directed agents,
Solution B, solution C and slurries D are added to the reaction mixture that synthesis NaY molecular sieve is made in water glass solution；To react mixing
The weight of object is 100wt% meter, and the additional amount of directed agents is 6wt%, obtains the reaction mixture of synthesis NaY, obtains synthesis NaY
Reaction mixture each component molar ratio are as follows: 6.2Na2O:Al2O3:12SiO2:260H2O mixes the reaction of NaY molecular sieve
Object crystallization 22h at 105 DEG C obtains Y/SAPO-34/ZSM-11 composite molecular screen slurries E.A certain amount of surfactant (is accounted for
1~6wt% of ASA weight) be added in Y/SAPO-34/ZSM-11 molecular sieve pulp E, be added while stirring alkaline silicon source or
Alkaline silicon source solution, and the pH value for being adjusted with acid system is 7~9, finally filters solid mixture matter obtained above, washes
It washs, 100 DEG C of dry 4h, 550 DEG C of roasting 6h, obtains mesoporous Y/SAPO-34/ZSM-11/ASA composite material.
Surfactant of the present invention mainly has tri- kinds of nonionic surfactants of CTAB, P123 and F127.
The silicon source used in the preparation process of Y/SAPO-34/ZSM-11/ASA composite material of the present invention is that this field is normal
, such as water glass solution.
Silicon source used in Y/SAPO-34/ZSM-11/ASA composite material preparation process of the present invention is this field
Commonly, such as sodium metaaluminate, boehmite, boehmite, aluminum nitrate, aluminum sulfate, aluminium hydroxide and/or gibbsite, alkali
Property silicon source be it is commonly used in the art, aluminium therein from sodium metaaluminate or can be dissolved in sodium hydroxide solution and intend thin water aluminium
Stone, boehmite, aluminium hydroxide, gibbsite, alkaline silicon source be it is commonly used in the art, silicon therein can derive from waterglass.
Acid is acid generally in the art, preferably inorganic acid, such as sulfuric acid, hydrochloric acid, nitric acid.
The content of Y molecular sieve is 10~80wt% in Y/SAPO-34/ZSM-11/ASA composite material of the present invention,
The content of SAPO-34 molecular sieve is 1~5wt%, and the content of ZSM-11 molecular sieve is 1~5wt%, remaining is sieve and silica-sesquioxide
(SiO2/Al2O3) and Al2O3、SiO2One 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/SAPO-34/ZSM-11/ASA composite material of the present invention
1008~1100 DEG C, the mesoporous average pore size of rule is 3~10nm, and total pore volume is 0.52~0.62mL/g, and Micropore volume is
0.20~0.30mL/g, mesoporous 0.27~0.40mL/g of Kong Rongwei.
In conclusion NaY molecular sieve has crystal grain small in Y/SAPO-34/ZSM-11 composite molecular screen produced by the present invention
(100~400nm), framework si-al ratio are high, thermal stability improve (5 DEG C higher than the differential thermal fail temperature of corresponding NaY molecular sieve with
On) and the mesoporous composition of rule less than the micropore of 1nm and 3~10nm micro--composite mesoporous pore structure the characteristics of.
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 of 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-FPrnigen 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.
The synthesis of embodiment 1:Y/SAPO-34/ZSM-11/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 of 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) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:1:5, by the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 2g be dispersed in 10g 5wt% potassium hydroxide and
In the aqueous solution of 5wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, SAPO-34 and ZSM-11 molecular sieve pulp is obtained,
Slurry pH value is adjusted to 7~8, SAPO-34 and ZSM-11 molecular sieve pulp D is obtained.
(3) preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3
Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (specification is same
Step 1), stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and slurries D according to
Conventional NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g in step 1) again after mixing evenly
The reaction mixture of synthesis NaY molecular sieve is made in water.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will
Reaction mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, and it is compound to obtain Y/SAPO-34/ZSM-11
Molecular sieve pulp E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal
Fail temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 0.8g sodium hydroxide is dissolved in 6.2g water, then
1g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution F is obtained.The Y/SAPO-34/ZSM-11 that step (3) is obtained
Molecular sieve and mother liquor are cooled to room temperature, and are transferred in beaker, static layering, upper layer mother liquor 32mL are taken out, then to Y/SAPO-
Surfactant P123 0.8g is added in the mix suspending object of 34/ZSM-11 molecular sieve and mother liquor and is stirred at 20 DEG C
Solution F is added in 30min later, continues to stir 1h after adding, sulfuric acid is added in the mixture of above-mentioned stirring, regulation system
PH value be 7.Finally solid matter obtained above is filtered, washed, 120 DEG C of dry 12h, 500 DEG C of roasting 4h, obtains Y/
SAPO-34/ZSM-11/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 is mesoporous, the aperture 5nm of rule, and the content of Y molecular sieve is 62wt%.Y/SAPO-34/ZSM-11/ASA composite material
The differential thermal fail temperature of middle NaY molecular sieve 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 28.7g 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: 17Na2O:Al2O3:16SiO2:330H2O。
(2) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:0.5:7, and the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 1g is dispersed in the 6wt% potassium hydroxide of 14g
In the aqueous solution of 5wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains SAPO-34 and ZSM-11 molecule screening the pulp
Slurry pH value is adjusted to 7~8, obtains SAPO-34 and ZSM-11 molecular sieve pulp D by liquid.
(3) preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3
Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (specification is same
Step 1), stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and slurries D according to
Conventional NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g in step 1) again after mixing evenly
The reaction mixture of synthesis NaY molecular sieve is made in water.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will
Reaction mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, and it is compound to obtain Y/SAPO-34/ZSM-11
Molecular sieve pulp E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal
Fail temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 7.5g sodium hydroxide is dissolved in 58g water, then
9.2g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution F is obtained.The Y/SAPO-34/ZSM- that step (3) is obtained
11 molecular sieves and mother liquor are cooled to room temperature, and are transferred in beaker, at 25 DEG C, sequentially add P123 1.6g, water glass while stirring
Glass 7.8g and solution F.Continue to stir 2h at 25 DEG C, nitric acid solution is added in the mixture of above-mentioned stirring, finally makes body
The pH value of system is 8.5.Finally solid matter obtained above is filtered, washed, 150 DEG C of dry 4h, 450 DEG C of roasting 10h, is obtained
Y/SAPO-34/ZSM-11/ASA composite material, intermediary hole part are sieve and silica-sesquioxide, and the molar ratio of sieve and silica-sesquioxide is 5:
1, mesoporous is mesoporous, the aperture 8nm of rule, and the content of Y molecular sieve is 35wt%.Y/SAPO-34/ZSM-11/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 20.7g 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 93g
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: 15Na2O:Al2O3:15SiO2:330H2O。
(2) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:0.75:3, and the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 1.5g is dispersed in the 7wt% hydroxide of 6g
In the aqueous solution of potassium and 5wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains SAPO-34 and ZSM-11 molecule screening the pulp
Slurry pH value is adjusted to 7~8, obtains SAPO-34 and ZSM-11 molecular sieve pulp D by liquid.
(3) preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3
Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (specification is same
Step 1), stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and slurries D according to
Conventional NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g in step 1) again after mixing evenly
The reaction mixture of synthesis NaY molecular sieve is made in water.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will
Reaction mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, and it is compound to obtain Y/SAPO-34/ZSM-11
Molecular sieve pulp E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal
Fail temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water,
16.1g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution F is obtained.The Y/SAPO-34/ that step (3) is obtained
ZSM-11 molecular sieve and mother liquor are cooled to room temperature, and mother liquor 90mL are taken out, then by remaining mother liquor and Y/SAPO-34/ZSM-11
In the beaker that the mixture of molecular sieve is transferred to, CTAB 6.5g and solution F is added while stirring at 18 DEG C, after adding solution F
Continue to stir 4h at 18 DEG C, hydrochloric acid solution is added in the mixture of above-mentioned stirring, the pH value of regulation system is 7.8.Finally
Solid matter obtained above is filtered, washed, 110 DEG C of dry 32h, 550 DEG C of roasting 6h, obtains Y/SAPO-34/ZSM-11/
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 to be situated between for rule
Hole, aperture 5.5nm, the content of Y type molecular sieve are 60wt%.NaY molecule in Y/SAPO-34/ZSM-11/ASA composite material
The differential thermal fail temperature of sieve 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 30.9g 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 107g
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:Al2O3:17SiO2:300H2O。
(2) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:0.5:5, and the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 1g is dispersed in the 6wt% potassium hydroxide of 10g
In the aqueous solution of 4wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains SAPO-34 and ZSM-11 molecule screening the pulp
Slurry pH value is adjusted to 7~8, obtains SAPO-34 and ZSM-11 molecular sieve pulp D by liquid.
(3) preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3
Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (specification is same
Step 1), stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and slurries D according to
Conventional NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g in step 1) again after mixing evenly
The reaction mixture of synthesis NaY molecular sieve is made in water.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will
Reaction mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, and it is compound to obtain Y/SAPO-34/ZSM-11
Molecular sieve pulp E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal
Fail temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g sodium hydroxide is dissolved in 37.6mL water,
4.4g aluminium hydroxide is added, stirring to aluminium hydroxide is all dissolved, and solution F is obtained.The Y/ containing mother liquor that step (3) is obtained
SAPO-34/ZSM-11 molecular sieve filtration, washing to washing water pH value be 9, then Y/SAPO-34/ZSM-11 molecular sieve is added
Water mashing, is added CTAB 4.8g while stirring at 20 DEG C, stirs 30min, then solution F and sulfuric acid, the pH value of regulation system
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/SAPO-34/
ZSM-11/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 to be
Mesoporous, the aperture 3.5nm of rule, the content of Y type molecular sieve are 60wt%.In Y/SAPO-34/ZSM-11/ASA composite material
1105 DEG C of the differential thermal fail temperature of NaY molecular 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 55.9g 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:Al2O3:16SiO2:350H2O。
(2) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:0.5:7, and the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 1g is dispersed in the 8wt% potassium hydroxide of 14g
In the aqueous solution of 5wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains SAPO-34 and ZSM-11 molecule screening the pulp
Slurry pH value is adjusted to 7~8, obtains SAPO-34 and ZSM-11 molecular sieve pulp D by liquid.
(3) preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g aluminum sulfate is dissolved in 50.6g water, forms Al2O3
Content is the aluminum sulfate solution B of 3.4wt%；4.5g sodium hydroxide is dissolved in 50.4g water, then plus 10g sodium metaaluminate (specification is same
Step 1), stirring form sodium aluminate solution C to being completely dissolved.By 10.3g directed agents, solution B, solution C and slurries D according to
Conventional NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g in step 1) again after mixing evenly
The reaction mixture of synthesis NaY molecular sieve is made in water.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will
Reaction mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, and it is compound to obtain Y/SAPO-34/ZSM-11
Molecular sieve pulp E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal
Fail temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 99.6g waterglass is poured into 171.4mL water, is obtained
Solution F.It is by the Y/SAPO-34/ZSM-11 molecular sieve filtration containing mother liquor that step (3) obtains, washing to the pH value of washing water
9, then add water to be beaten in Y/SAPO-34/ZSM-11 molecular sieve, the F127 and solution F of 3.8g is added 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/SAPO-34/ZSM-11/ASA composite material, the molar ratio of sieve and silica-sesquioxide is 4.5:1, mesoporous for rule
Then mesoporous, aperture 6.5nm, the content of Y type molecular sieve is 65wt%.NaY in Y/SAPO-34/ZSM-11/ASA composite material
1008 DEG C of the differential thermal fail temperature of molecular sieve, 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) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:0.75:3, and the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 1.5g is dispersed in the 8wt% hydroxide of 6g
In the aqueous solution of potassium and 5wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains SAPO-34 and ZSM-11 molecule screening the pulp
Slurry pH value is adjusted to 7~8, obtains SAPO-34 and ZSM-11 molecular sieve pulp D by liquid.
(3) 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, solution C and slurries D according to routine
NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g water in step 1) again after mixing evenly, makes
At the reaction mixture of synthesis NaY molecular sieve.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will reaction
Mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, obtains Y/SAPO-34/ZSM-11 compound molecule
Screening the pulp liquid E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal destroy
Temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water,
4.4g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution F is obtained.The Y/SAPO-34/ that step (3) is obtained
ZSM-11 molecular sieve and mother liquor are cooled to room temperature, and mother liquor 180mL are taken out, then by remaining mother liquor and Y/SAPO-34/ZSM-11
The mixture of molecular sieve is transferred in plastic beaker, sequentially added while stirring at 30 DEG C P123 1.3g, SAPO-34 with
ZSM-11 molecular sieve pulp E, solution D and sulfuric acid, the pH value of regulation system are 7.5.Finally by solid mixture obtained above
Matter is filtered, washed, 130 DEG C of dry 8h, 650 DEG C of roasting 4h, obtains Y/SAPO-34/ZSM-11/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, and mesoporous is mesoporous, the aperture 9.5nm of rule, with
On the basis of Y/SAPO-34/ZSM-11/ASA composite material, the content of Y type molecular sieve is 80wt%.Y/SAPO-34/ZSM-11/
1055 DEG C of the differential thermal fail temperature of NaY molecular sieve in ASA composite material, texture property 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 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 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:Al2O3:16SiO2:300H2O。
(2) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:1:7, by the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 2g be dispersed in 14g 9wt% potassium hydroxide and
In the aqueous solution of 4wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, SAPO-34 and ZSM-11 molecular sieve pulp is obtained,
Slurry pH value is adjusted to 7~8, SAPO-34 and ZSM-11 molecular sieve pulp D is obtained.
(3) 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, solution C and slurries D according to routine
NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g water in step 1) again after mixing evenly, makes
At the reaction mixture of synthesis NaY molecular sieve.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will reaction
Mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, obtains Y/SAPO-34/ZSM-11 compound molecule
Screening the pulp liquid E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal destroy
Temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water,
8.8g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution F is obtained.The Y/SAPO-34/ that step (3) is obtained
ZSM-11 molecular sieve and mother liquor are cooled to room temperature, and mother liquor 200mL are taken out, then by remaining mother liquor and Y/SAPO-34/ZSM-11
The mixture of molecular sieve is transferred in beaker, and P123 0.8g and F127 4.2g is added while stirring at 25 DEG C and stirs evenly
Afterwards, solution F and sulfuric acid are sequentially added, the pH value of regulation system is 8.0.Finally solid matter obtained above is filtered, is washed
It washs, 120 DEG C of dry 12h, 550 DEG C of roasting 4h, obtains Y/SAPO-34/ZSM-11/ASA composite material, intermediary hole part is silicon
Aluminum oxide, the silica alumina ratio of sieve and silica-sesquioxide are 1.5:1, and mesoporous is mesoporous, the aperture 9.2nm, with Y/SAPO- of rule
On the basis of 34/ZSM-11/ASA composite material, the content of Y type molecular sieve is 80wt%.Y/SAPO-34/ZSM-11/ASA is compound
1027 DEG C of the differential thermal fail temperature of NaY molecular sieve in material, 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 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) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:0.5:3, and the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 1g is dispersed in the 10wt% potassium hydroxide of 6g
In the aqueous solution of 2wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, obtains SAPO-34 and ZSM-11 molecule screening the pulp
Slurry pH value is adjusted to 7~8, obtains SAPO-34 and ZSM-11 molecular sieve pulp D by liquid.
(3) 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, solution C and slurries D according to routine
NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g water in step 1) again after mixing evenly, makes
At the reaction mixture of synthesis NaY molecular sieve.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will reaction
Mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, obtains Y/SAPO-34/ZSM-11 compound molecule
Screening the pulp liquid E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal destroy
Temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water,
8.8g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution F is obtained.The Y/SAPO-34/ that step (3) is obtained
ZSM-11 molecular sieve and mother liquor are cooled to room temperature, and mother liquor 220mL are taken out, then by remaining mother liquor and Y/SAPO-34/ZSM-11
The mixture of molecular sieve is transferred in beaker, and P123 1.2g and CTAB 3.8g is added while stirring at 25 DEG C, stirs evenly
Afterwards, solution F and sulfuric acid are sequentially added, the pH value of regulation system is 8.0.Finally solid matter obtained above is filtered, is washed
It washs, 120 DEG C of dry 12h, 550 DEG C of roasting 4h, obtains Y/SAPO-34/ZSM-11/ASA composite material, intermediary hole part is silicon
Aluminum oxide, the silica alumina ratio of sieve and silica-sesquioxide are 1:1, and mesoporous mesoporous for rule, aperture 7.5nm, Y type molecular sieve contains
Amount is 80wt%.1034 DEG C of the differential thermal fail temperature of NaY molecular sieve, texture in Y/SAPO-34/ZSM-11/ASA composite material
Matter 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 55.9g 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:Al2O3:16SiO2:350H2O。
(2) prepared by SAPO-34 and ZSM-11 molecular sieve pulp: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: water-soluble
Liquid proportional is 1:1:5, by the ZSM-11 molecular sieve of the SAPO-34 molecular sieve of 2g and 2g be dispersed in 10g 5wt% potassium hydroxide and
In the aqueous solution of 5wt% boric acid, 70~80 DEG C are heated to, constant temperature stirs 2h, SAPO-34 and ZSM-11 molecular sieve pulp is obtained,
Slurry pH value is adjusted to 7~8, SAPO-34 and ZSM-11 molecular sieve pulp D is obtained.
(3) 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, solution C and slurries D according to routine
NaY molecular sieve preparation step is added sequentially to 75g waterglass, and (specification adds 48.5g water in step 1) again after mixing evenly, makes
At the reaction mixture of synthesis NaY molecular sieve.The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O；It will reaction
Mixture is gone in autoclave, and crystallization 22h, hydrothermal crystallizing finish at 105 DEG C, obtains Y/SAPO-34/ZSM-11 compound molecule
Screening the pulp liquid E.Wherein the relative crystallinity of NaY molecular sieve be 95%, framework si-al ratio 5.2, partial size 200nm, differential thermal destroy
Temperature is 950 DEG C.
(4) preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g sodium hydroxide is dissolved in 27.6g water,
8.8g sodium metaaluminate is added, stirring to sodium metaaluminate is all dissolved, and solution F is obtained.The Y/SAPO-34/ that step (2) is obtained
ZSM-11 molecular sieve and mother liquor are cooled to room temperature, and mother liquor 200mL are taken out, then by remaining mother liquor and Y/SAPO-34/ZSM-11
The mixture of molecular sieve is transferred in plastic beaker, CTAB 4.2g and F127 8.2g is added while stirring at 25 DEG C, successively
Solution F and sulfuric acid is added, the pH value of regulation system is 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/SAPO-34/ZSM-11/ASA composite material, and intermediary hole part is sieve and silica-sesquioxide,
The silica alumina ratio of sieve and silica-sesquioxide is 1.5:1, and mesoporous mesoporous for rule, the content of aperture 7.3nm, Y type molecular sieve are
70wt%.1050 DEG C of the differential thermal fail temperature of NaY molecular sieve in Y/SAPO-34/ZSM-11/ASA 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 of 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) preparation of Y/ASA composite material: in addition to surfactant is not added, with (4) the step of embodiment 1.Mesoporous hole
Diameter is 3.3~5.2nm.910 DEG C of the differential thermal fail temperature of NaY molecular sieve in Y/ASA composite material, 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,
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) preparation of Y/ASA composite material: with (4) the step of embodiment 4, CTAB is not added.Mesoporous part is sial oxygen
Compound, silica alumina ratio 5.5:1, mesoporous aperture are 3.2~6.5nm, and the differential thermal of NaY molecular sieve destroys in Y/ASA composite material
1050 DEG C of temperature, 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 destroys temperature in Y/ASA composite material
985 DEG C of degree, texture property is shown in Table 1.
The texture property of NaY in table 1Y/SAPO-34/ZSM-5/ASA composite material
The Y/SAPO-34/ZSM-11/ASA composite wood prepared it can be seen from the result of table 1 using method of the invention
The differential thermal fail temperature of NaY molecular sieve in material is improved.Y/SAPO-34/ZSM-11/ASA prepared by the present invention is multiple
Condensation material has biggish total pore volume and mesoporous Kong Rong, and mesoporous average pore size is 3~10nm and is regular meso-hole structure, to have
The conversion of machine macromolecular provides open space, is conducive to the Efficient Conversion of heavy oil molecules.And in composite material preparation process,
The random distribution of mesoporous pore size of composite material for being not added with surface-active and preparing.
Claims (10)
1. a kind of preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material, includes the following steps:
(1) directed agents are prepared:
Sodium hydroxide and silicon source are added to the water, or aluminium 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
Mix it is lower solution A and water glass solution are added sequentially in deionized water, after mixing evenly, the static ageing at 15~50 DEG C
Directed agents are made in 0.5~60h；The molar ratio of each component is Na in directed agents2O:Al2O3:SiO2:H2O=15~17:1:15~
17:300~350；
(2) preparation of slurries D:
According to SAPO-34 molecular sieve: ZSM-11 molecular sieve: aqueous solution mass ratio is 1:0.5~1:3~7, by SAPO-34 and
ZSM-11 molecular sieve disperses in aqueous solution, to be heated to 70~80 DEG C, and constant temperature stirs 2~5h, obtains SAPO-34 and ZSM-11 points
Sub- screening the pulp liquid adjusts the pH value of SAPO-34 and ZSM-11 molecular sieve pulp, obtains SAPO-34 and ZSM-11 molecular sieve pulp D；
The aqueous solution is the aqueous solution of 1~10wt% potassium hydroxide and 1~5wt% boric acid；
(3) preparation of Y/SAPO-34/ZSM-11 composite molecular screen slurries E:
Silicon source is dissolved in water, Al is formed2O3Content is the solution B of 1~4wt%；
Sodium hydroxide is added to the water with silicon source or aluminium hydroxide is added to the water to after being completely dissolved and adds silicon source,
Form sodium aluminate solution C, Al in solution C2O3Content be 3~9wt%, Na2O content is 1~20wt%；
The directed agents, solution B, solution C and slurries D are added to the reaction that synthesis NaY molecular sieve is made in water glass solution
Mixture；By the weight of reaction mixture for 100wt% in terms of, the additional amounts of directed agents is 0.5~20wt%, obtains synthesis NaY
Reaction mixture each component molar ratio are as follows: Na2O:Al2O3:SiO2:H2O=4~8:1:10~15:200~300；
After reaction mixture crystallization, Y/SAPO-34/ZSM-11 composite molecular screen slurries E is obtained；
(4) preparation of Y/SAPO-34/ZSM-11/ASA multilevel hole material
Surfactant is added in the Y/SAPO-34/ZSM-11 composite molecular screen slurries E, alkaline silicon source or alkali are added
Property silicon source solution, and it is adjusted with acid the pH value of system, finally obtained solid mixture matter is filtered, washed, dry, is roasted,
Obtain Y/SAPO-34/ZSM-11/ASA multilevel hole material.
2. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (4), the surfactant is at least one of CTAB, P123 and F127.
3. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (4), the additional amount of the surfactant be account for Y/SAPO-34/ZSM-11/ASA multilevel hole material weight 1~
3wt%.
4. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (2), the pH value is 7~8.
5. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (4), the pH value is 7~9.
6. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (3), the condition of crystallization are as follows: 8~48h of crystallization at 80~140 DEG C.
7. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (1) and (3), source of aluminium is sodium metaaluminate, boehmite, boehmite, aluminum nitrate, aluminum sulfate, aluminium hydroxide
One or more of with gibbsite.
8. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (4), it is described alkalinity silicon source be sodium metaaluminate, or be dissolved in sodium hydroxide solution boehmite, boehmite,
Aluminium hydroxide or gibbsite.
9. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, it is characterised in that:
In step (4), the acid is sulfuric acid, hydrochloric acid or nitric acid.
10. the preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material according to claim 1, feature exist
In: mesoporous mesoporous for rule in the Y/SAPO-34/ZSM-11/ASA multilevel hole material, total pore volume is 0.52~0.62mL/
G, Micropore volume are 0.20~0.30mL/g, mesoporous 0.27~0.40mL/g of Kong Rongwei.
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