CN109205636B - Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material - Google Patents
Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material Download PDFInfo
- Publication number
- CN109205636B CN109205636B CN201710519563.5A CN201710519563A CN109205636B CN 109205636 B CN109205636 B CN 109205636B CN 201710519563 A CN201710519563 A CN 201710519563A CN 109205636 B CN109205636 B CN 109205636B
- Authority
- CN
- China
- Prior art keywords
- zsm
- sapo
- molecular sieve
- solution
- asa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 272
- 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 271
- 239000002131 composite material Substances 0.000 claims abstract description 106
- 239000002002 slurry Substances 0.000 claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 186
- 239000000243 solution Substances 0.000 claims description 143
- 239000011734 sodium Substances 0.000 claims description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 97
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 95
- 229910052708 sodium Inorganic materials 0.000 claims description 95
- 238000003756 stirring Methods 0.000 claims description 93
- 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 49
- 229910052593 corundum Inorganic materials 0.000 claims description 47
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 47
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 41
- 235000019353 potassium silicate Nutrition 0.000 claims description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- 239000011541 reaction mixture Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 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 16
- 230000032683 aging Effects 0.000 claims description 15
- 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 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910001679 gibbsite Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 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
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 description 28
- 239000012452 mother liquor Substances 0.000 description 25
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 21
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- 230000006378 damage Effects 0.000 description 16
- 239000002994 raw material Substances 0.000 description 11
- 239000001164 aluminium sulphate Substances 0.000 description 10
- 235000011128 aluminium sulphate Nutrition 0.000 description 10
- 229940024545 aluminum hydroxide Drugs 0.000 description 10
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 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
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000003786 synthesis reaction 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
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000012258 stirred mixture Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method 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
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 208000033498 Non-syndromic pontocerebellar hypoplasia Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 208000017262 paroxysmal cold hemoglobinuria Diseases 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical porous material, which is characterized by comprising the following steps: firstly synthesizing a guiding agent, synthesizing a Y/SAPO-34/ZSM-11 composite molecular sieve by adopting a hydrothermal crystallization method, then adding a surfactant, an alkaline aluminum source and/or an alkaline silicon source solution into slurry of the Y/SAPO-34/ZSM-11 molecular sieve, washing, drying and roasting a product to obtain the mesoporous Y/SAPO-34/ZSM-11/ASA hierarchical pore material.
Description
Technical Field
The invention provides a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical porous material, which comprises the steps of firstly synthesizing a guiding agent, synthesizing a Y/SAPO-34/ZSM-11 composite molecular sieve by adopting a hydrothermal crystallization method, then adding a surfactant, an alkaline aluminum source and/or an alkaline silicon source solution into slurry of the Y/SAPO-34/ZSM-11 molecular sieve, washing, drying and roasting a product to obtain the mesoporous Y/SAPO-34/ZSM-11/ASA composite material.
Background
The molecular sieve complex is a composite material formed by combining a molecular sieve and other substances through the action of molecules, atoms or ions. Regular materials with mesoporous structures, such as MCM-41 mesoporous molecular sieves, are suitable for the conversion of organic macromolecules due to the large pore structure, but the application of the materials in the field of catalysis is limited by the poor thermal stability, hydrothermal stability and weak acidity of the regular materials. The research of the microporous-mesoporous composite material based on the high-stability and strong-acid microporous molecular sieve has important industrial application value.
With the continuous development of molecular sieve catalysis application, the molecular sieve with a single pore channel can not meet the preparation requirements of various catalysts. The microporous molecular sieve is mainly characterized by stronger acid property and higher structural stability in the heterogeneous catalysis application, but because the pore size of the microporous molecular sieve is smaller and the pore channel is slender, the macromolecules in the reaction raw materials such as heavy oil are difficult to diffuse into the pore channel, so the utilization rate of the acid sites in the pore channel of the microporous molecular sieve can be reduced, and meanwhile, the diffusion resistance of the narrow and slender pore channel is higher, the rapid diffusion overflow of the reaction product molecules is influenced, and deep cracking and coking are easily caused. Although mesoporous molecular sieves can make up for the limitation of microporous molecular sieves on the internal diffusion of reactants and reaction products, mesoporous molecular sieves are often poor in structural stability and also limit the catalytic application of mesoporous molecular sieves.
CN 200810012192 provides a preparation method of a Y molecular sieve/silicon dioxide composite material, which is to uniformly mix a Y-type molecular sieve, sodium hydroxide, distilled water, a template agent and a silicon source under the stirring state to prepare reaction mixture gel, wherein the molar ratio of each component is as follows: (0-1.3) Na2O:(34.4-110)H2O:(0.75-11.3)SiO2R is a template agent (0.046-0.7). The gel is crystallized for 12-70 h at 80-180 ℃, and the core-shell composite material is obtained after suction filtration and washing. Content of Y molecular sieve in composite material10-30 wt%, the particle size of the composite material is 2-10 μm. In the method, the Y-type molecular sieve does not participate in the growth of the attached crystal of the silicon dioxide, no chemical bond action exists between the Y-type molecular sieve and the silicon dioxide, the silicon dioxide can not provide acidity, and the Y-type molecular sieve can only play a role in shape selection in various catalytic reactions, so that the acidity of the composite material can only be realized by modulating the Y-type molecular sieve. But mesopores are irregular and hierarchical pores.
Liu et al, in the Journal of American Chemical Society (2000,122:8791-8792), describe a method for preparing mesoporous materials using Y molecular sieve secondary building blocks: firstly, NaOH, NaAlO2, H2O and water glass are mixed to prepare Y molecular sieve seed crystal solution containing 27 wt% of SiO2 and 14 wt% of NaOH, template agent CTAB and dilute sulfuric acid solution are introduced into the seed crystal solution, the pH value of the seed crystal solution is adjusted to be 9, the seed crystal solution is crystallized for 20 hours at 100 ℃, and secondary structural units of the Y molecular sieve in the seed crystal solution in the crystallization process are assembled into a composite material with a hexagonal mesoporous structure under the action of the template agent CTAB, namely Al-MSU-S. The mesoporous material is assembled by using the Y-type molecular sieve, but the mesoporous wall of the micro-mesoporous composite material is of an amorphous structure, and the hydrothermal stability of the micro-mesoporous composite material is poor.
Zhang et al describe a method for preparing Y/MCM-48 micro-mesoporous composites in the Applied Catalysis A: General (2008,345: 73-79): adding NaY crystal seeds into MCM-48 precursor sol, wherein the precursor solution comprises the following other materials: 0.415CTAB to 0.48NaOH to 55H2O to 1TEOS, stirring the mixed solution for 50 minutes, performing hydrothermal crystallization for a period of time at 110 ℃, performing suction filtration and washing to obtain a solid product, and roasting for 6 hours at 550 ℃ in an air atmosphere to obtain the Y/MCM-48 composite molecular sieve. Although the thickness of the mesoporous wall of the MCM-48 molecular sieve prepared by the method is increased, the mesoporous wall is still in an amorphous structure, so that the poor hydrothermal stability is still an important reason for restricting the application of the molecular sieve.
CN102000604A provides a method for preparing a Y/MCM-41 composite molecular sieve by a microwave method by taking kaolin as a raw material and inorganic silicate as a silicon source. Firstly, kaolin is taken as a raw material, a certain amount of sodium silicate is added to synthesize a precursor of the Y-type molecular sieve, and then hexadecyl trimethyl ammonium bromide is taken as a template agent to prepare the composite molecular sieve Y/MCM-41 by a microwave method. The synthesized Y/MCM-41 composite molecular sieve has a micro-mesoporous double-pore structure, the specific surface area of a sample is more than 550m2/g, the average pore diameter is about 2.7nm, and the sample has a regular and ordered hexagonal mesoporous structure. Although the MCM-41 molecular sieve prepared by the method has the structure that secondary structural units of the Y-type molecular sieve are introduced into the sieve pore wall, the thermal stability is still insufficient, and the collapse temperature is lower than 800 ℃.
CN101172244 provides a preparation method of a montmorillonite/Y molecular sieve composite material. Montmorillonite particles and Y molecular sieve gel are uniformly mixed, then crystallization is carried out, and the montmorillonite/Y molecular sieve composite material is prepared by filtering, washing and drying. The composite material prepared by the method has the structural characteristics of montmorillonite and Y molecular sieve, wherein the montmorillonite and the Y molecular sieve are intergrowth, and the Y molecular sieve grows on the montmorillonite microspheres, but the framework silicon-aluminum ratio of the Y molecular sieve in the composite material prepared by the method is lower, so that the hydrothermal stability of the composite material is possibly poor.
CN101172243 provides a preparation method of mesoporous/microporous molecular sieve composite material, the composite material is prepared by mixing porous clay isomeric material (PCHs) and microporous molecular sieve gel for in-situ crystallization, in the composite material prepared by the invention, the microporous molecular sieve is wrapped around the porous clay isomeric material, the composite material has the crystal structure of the microporous molecular sieve and the mesoporous structure of the porous clay isomeric material at the same time, and belongs to a double-pore composite material, the Y-type, ZSM-5 type, β type microporous molecular sieves can be obtained by crystallization according to different gel proportions in the composite material, and the stability of the composite material prepared by the method is poor.
CN200610165597.0 provides a preparation method of a nano molecular sieve/silicon-aluminum oxide composite catalytic material, which comprises the steps of firstly synthesizing a nano molecular sieve by adopting a guide agent method, treating the nano molecular sieve by adopting microwave and/or ultrasonic waves in a precipitation step in the synthesis, then adding a mixture aqueous solution of water glass and an aluminum source into slurry containing the nano molecular sieve, and adding acid to adjust the pH value to 7-9.5 to form gel; and drying and roasting the gel to obtain the composite catalytic material, wherein an aluminum source is selected from sodium metaaluminate or aluminum sulfate, the method ensures that the particles of the molecular sieve product are kept below 100nm, and the nano molecular sieve is not easy to aggregate, so that the molecular sieve is prevented from being damaged by acid without an acid sol process. The composite material is suitable for catalytic cracking and hydrocracking reactions of heavy oil macromolecules.
Prndau et al describe a method for in-situ synthesis of nano molecular sieve ZSM-5 in the pore channels of silica gel in Applied Catalysis A: General (1994,115: L7-L14), wherein zeolite with a particle size of 3-5 μm is formed on the outer surface of silica gel, zeolite with a particle size of 0.5-2 μm is formed in the macropores of silica gel, and zeolite with a particle size of 0.02-0.035 μm is formed in the mesopores of silica gel.
Prndau et Al, in chem.Mater (1999,11:2030-2037), describe a method for stabilizing β molecular sieves having a particle size of 10-15nm in an aluminum sol by first dispersing an aluminum hydroxide gel filter cake in water to form an aluminum hydroxide emulsion having a pH of 9.05 and then slurrying β molecular sieves having a pH of 12.7 at room temperature as Al2O3Molecular sieve/1 to pH 11.8 (in the preparation of two additional samples dilute nitric acid was added after said mixing to pH 11.0 and 10.0, respectively, after mixing); after stirring for 2h, aging for 24h at room temperature; the precipitate was separated by decantation and dried in vacuo at 50 ℃ to a water content of 70% by weight. Extrusion granulation and drying at 120 ℃ for 5h, then temperature programmed roasting. The disadvantage of this process is the long preparation time.
The preparation methods of the micro-mesoporous composite materials mentioned in the above documents or patents are either complicated in process or long in synthesis process time. The CN102000604A introduces a microwave treatment process in the process of synthesizing the Y/MCM-41 composite molecular sieve, adds auxiliary equipment and greatly increases the cost of synthesizing the composite molecular sieve. In addition, the mesoporous portion in the micro-mesoporous composite material mentioned in the above documents or patents is irregular pores. In the above patents, heteropoly acid is generally supported or mixed with macroporous amorphous structure materials such as alumina, silica-alumina, etc., but these materials have relatively low specific surface area compared with regular ordered mesoporous materials, and the catalytic reaction activity of heteropoly acid is reduced. The microporous molecular sieve has a small pore diameter, while the heteropoly acid molecule is relatively large, and thus the specific surface area and pore volume loss after loading are large, and the catalytic activity is difficult to exert. The mesoporous molecular sieves developed in recent years have greatly improved specific surface area, pore volume and pore diameter, but mesoporous molecular sieves such as SBA-15 and MCM-41 have poor thermal stability, and the framework structure is easy to collapse and permanently loses catalytic activity under long-term high-temperature conditions.
Disclosure of Invention
The invention aims to develop a Y/SAPO-34/ZSM-11/ASA hierarchical porous material, which is prepared by firstly synthesizing a guiding agent, synthesizing a Y/SAPO-34/ZSM-11 composite molecular sieve by adopting a hydrothermal crystallization method, then adding a surfactant, an alkaline aluminum source and/or an alkaline silicon source solution into slurry of the Y/SAPO-34/ZSM-11 molecular sieve, washing, drying and roasting a product to obtain the mesoporous Y/SAPO-34/ZSM-11/ASA composite material.
The invention provides a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps:
(1) preparing a guiding agent:
adding sodium hydroxide and an aluminum source into water, or adding the aluminum hydroxide into the water until the aluminum hydroxide is completely dissolved, and then adding the aluminum source to form a sodium metaaluminate solution A, wherein Al in the solution A2O32.5-10 wt% of Na2The content of O is 8-35 wt%; sequentially adding the solution A and the water glass solution into deionized water under stirring, uniformly stirring, and standing and aging at 15-50 ℃ for 0.5-60 h to prepare a guiding agent; the molar ratio of each component in the guiding agent is Na2O:Al2O3:SiO2:H2O＝15～17:1:15～17:250～350；
(2) Preparation of slurry D:
according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: dispersing SAPO-34 and ZSM-11 molecular sieves in an aqueous solution according to the mass ratio of 1: 0.2-5: 3-7, heating to 70-80 ℃, stirring at a constant temperature for 2-5 h to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and adjusting the pH values of the SAPO-34 and ZSM-11 molecular sieve slurry to obtain SAPO-34 and ZSM-11 molecular sieve slurry D;
the aqueous solution is an aqueous solution of 1-10 wt% of potassium hydroxide and 1-5 wt% of boric acid;
(3) preparing Y/SAPO-34/ZSM-11 composite molecular sieve slurry E:
dissolving an aluminum source in waterIn (1), Al is formed2O31-4 wt% of solution B;
adding sodium hydroxide and an aluminum source into water, or adding the aluminum source into the water after the aluminum hydroxide is completely dissolved to form a sodium metaaluminate solution C, wherein Al in the solution C2O3Is 3 to 9 wt% of Na2The content of O is 1-20 wt%;
adding the guiding agent, the solution B, the solution C and the slurry D into a water glass solution to prepare a reaction mixture for synthesizing the NaY molecular sieve; the addition amount of the guiding agent is 0.5-20 wt% based on 100wt% of the reaction mixture, and the molar ratio of each component of the reaction mixture for synthesizing NaY is as follows: na (Na)2O:Al2O3:SiO2:H2O＝4～8:1:10～15:200～300；
Crystallizing the reaction mixture to obtain Y/SAPO-34/ZSM-11 composite molecular sieve slurry E;
(4) preparation of Y/SAPO-34/ZSM-11/ASA hierarchical pore material
Adding a surfactant into the Y/SAPO-34/ZSM-11 composite molecular sieve slurry E, adding an alkaline aluminum source or alkaline silicon source solution, adjusting the pH value of the system by using acid, and finally filtering, washing, drying and roasting the obtained solid mixed substance to obtain the Y/SAPO-34/ZSM-11/ASA hierarchical porous material.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in the step (4), the surfactant is preferably at least one of CTAB, P123 and F127.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in the step (4), the addition amount of the surfactant is preferably 1-3 wt% of the weight of the Y/SAPO-34/ZSM-11/ASA hierarchical porous material.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in the step (2), the pH value is preferably 7-8.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in the step (4), the pH value is preferably 7-9.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in the step (3), the crystallization conditions are preferably as follows: crystallizing at 80-140 ℃ for 8-48 h.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in the steps (1) and (3), the aluminum source is preferably one or more of sodium metaaluminate, pseudo-boehmite, aluminum nitrate, aluminum sulfate, aluminum hydroxide and gibbsite.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in step (4), the alkali aluminum source is preferably sodium metaaluminate, or pseudo-boehmite, aluminum hydroxide or gibbsite dissolved in a sodium hydroxide solution.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: in step (4), the acid is preferably sulfuric acid, hydrochloric acid or nitric acid.
The invention relates to a preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical pore material, which comprises the following steps: the mesopores in the Y/SAPO-34/ZSM-11/ASA hierarchical pore material are regular mesopores, the total pore volume is 0.52-0.62 mL/g, the micropore volume is 0.20-0.30 mL/g, and the mesopore volume is 0.27-0.40 mL/g.
The invention can also be detailed as follows:
a preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical porous material, which is used for preparing heavy naphtha and aviation kerosene hydrocracking catalyst, comprises the following steps:
1. preparing a guiding agent: adding sodium hydroxide and an aluminum source into water, or adding the sodium hydroxide into the water to dissolve the sodium hydroxide and then adding the aluminum source to form a sodium metaaluminate solution A, wherein Al in the solution A2O3Is 3.8 wt% of Na2The O content is 20 wt%; adding the solution A into a water glass solution under stirring, uniformly stirring, and standing and aging at 30 ℃ for 3 hours to prepare a guiding agent; the molar ratio of each component in the guiding agent is 16Na2O:Al2O3:16SiO2:330H2O。
2. Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the ratio of the aqueous solution is 1:1:5, SAPO-34 and ZSM-11 molecular sieves are dispersed in 1-10 wt% of potassium hydroxide and 1-5 wt% of boric acid, heated to 70-80 ℃, stirred at a constant temperature for 2 hours to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and the pH value is adjusted to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
3. Preparation of Y/SAPO-34/ZSM-11/ASA: dissolving a water-soluble aluminum source in water to form Al2O3Solution B with a content of 2 wt%; adding sodium hydroxide and an aluminum source into water, or adding the sodium hydroxide into the water to dissolve the sodium hydroxide and then adding the aluminum source to form a sodium metaaluminate solution C, wherein Al in the solution C2O3Is 6.5 wt% Na2The O content is 13.2 wt%; adding a guiding agent, the solution B, the solution C and the slurry D into a water glass solution to prepare a reaction mixture for synthesizing the NaY molecular sieve; the addition amount of the guiding agent is 6 wt% based on 100wt% of the reaction mixture, so as to obtain a reaction mixture for synthesizing NaY, wherein the molar ratio of each component of the reaction mixture for synthesizing NaY is as follows: 6.2Na2O:Al2O3:12SiO2:260H2And O, crystallizing the reaction mixture of the NaY molecular sieve at 105 ℃ for 22h to obtain Y/SAPO-34/ZSM-11 composite molecular sieve slurry E. Adding a certain amount of surfactant (accounting for 1-6 wt% of the ASA weight) into Y/SAPO-34/ZSM-11 molecular sieve slurry E, adding an alkaline aluminum source or alkaline silicon source solution while stirring, adjusting the pH value of the system to 7-9 with acid, filtering and washing the obtained solid mixed substance, drying at 100 ℃ for 4h, and roasting at 550 ℃ for 6h to obtain the mesoporous Y/SAPO-34/ZSM-11/ASA composite material.
The surfactant mainly comprises three nonionic surfactants of CTAB, P123 and F127.
The silicon source used in the preparation of the Y/SAPO-34/ZSM-11/ASA composite of the invention is conventional in the art, such as a water glass solution.
The aluminum source used in the preparation process of the Y/SAPO-34/ZSM-11/ASA composite material is commonly used in the field, such as sodium metaaluminate, pseudo-boehmite, aluminum nitrate, aluminum sulfate, aluminum hydroxide and/or gibbsite, the alkaline aluminum source is commonly used in the field, wherein the aluminum can be derived from sodium metaaluminate or pseudo-boehmite, aluminum hydroxide and gibbsite dissolved in sodium hydroxide solution, the alkaline silicon source is commonly used in the field, and the silicon can be derived from water glass. The acid is commonly used in the art, and is preferably an inorganic acid, such as sulfuric acid, hydrochloric acid, nitric acid, and the like.
The Y/SAPO-34/ZSM-11/ASA composite material contains 10-80 wt% of Y molecular sieve, 1-5 wt% of SAPO-34 molecular sieve, 1-5 wt% of ZSM-11 molecular sieve and the balance of silicon-aluminum oxide (SiO)2/Al2O3) And Al2O3、SiO2SiO of silicon-aluminum oxide2With Al2O3The molar ratio of (B) is preferably 1:1 to 10: 1.
The differential thermal destruction temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material can reach 1008-1100 ℃, the average pore diameter of regular mesopores is 3-10 nm, the total pore volume is 0.52-0.62 mL/g, the micropore volume is 0.20-0.30 mL/g, and the mesopore volume is 0.27-0.40 mL/g.
In conclusion, the NaY molecular sieve in the Y/SAPO-34/ZSM-11 composite molecular sieve prepared by the invention has the characteristics of small crystal grains (100-400 nm), high framework silicon-aluminum ratio, improved thermal stability (higher than the differential thermal failure temperature of the corresponding NaY molecular sieve by more than 5 ℃), and micro-mesoporous composite pore structure consisting of micropores smaller than 1nm and regular mesopores of 3-10 nm.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The analysis and test method comprises the following steps:
the relative crystallinity and the framework Si/Al ratio of the NaY molecular sieve were determined by using a D8 advanced X-ray diffractometer manufactured by Bruker, Germany, under the conditions of irradiation with CuK α, tube pressure of 40kV, and tube current of 40 mA., according to the SH/T0340-92 standard method (see "chemical industry standards Association", China standards Press, published 2000), and the framework Si/Al ratio was determined according to the SH/T0399-92 standard method (see "chemical industry standards Association", China standards Press, published 2000) and according to the following formula:
the unit cell constant a of the NaY molecular sieve was calculated.
Then according to the formula Breck-FPrnigen:
and calculating the framework silicon-aluminum ratio of the NaY molecular sieve.
SEM analysis Using a model 435VP scanning electron microscope manufactured by LEO of UK, an accelerating voltage of 20kV, and a sample was plated with gold by a physical method before the test.
The thermal stability was measured on a thermal analyzer model STA 409PC from the German Steady instruments. The experiment was carried out in Ar atmosphere, the temperature rise rate was 10 ℃/min, the temperature range: room temperature to 1200 ℃.
Specific surface area and pore volume test: the measurement of the specific surface area and pore structure of the catalyst and the molecular sieve was carried out on an ASAP2020M specific surface area and porosity analyzer manufactured by Micromeritics, and the specific surface area was calculated according to the BET method; the BJH method calculates pore volume.
Example 1: synthesis of Y/SAPO-34/ZSM-11/ASA composite material
(1) Preparation of a guiding agent: adding 24.7g sodium hydroxide (analytically pure, Beijing chemical plant) into 45.9g water, stirring until sodium hydroxide is completely dissolved, adding 6.5g sodium metaaluminate (Shandong aluminum industry institute, Industrial product, Al)2O3Content 49.1 wt%), stirring until sodium metaaluminate is completely dissolved, and obtaining sodium metaaluminate solution A. 70g of solution A and 100g of water glass (Beijing Hongxing soda plant, SiO)2Content 27.81 wt%, Na2O content of 8.74 wt%) are poured into 65.5g of deionized water in turn, stirred uniformly and then kept stand and aged for 22h at 30 DEG CAnd obtaining the guiding agent. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the ratio of the aqueous solution is 1:1:5, dispersing 2g of SAPO-34 molecular sieve and 2g of ZSM-11 molecular sieve in 10g of aqueous solution of 5wt% of potassium hydroxide and 5wt% of boric acid, heating to 70-80 ℃, stirring at constant temperature for 2h to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and adjusting the pH value of the slurry to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that in step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 0.8g of sodium hydroxide is dissolved in 6.2g of water, 1g of sodium metaaluminate is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved, so that a solution F is obtained. And (3) cooling the Y/SAPO-34/ZSM-11 molecular sieve and the mother liquor obtained in the step (3) to room temperature, transferring the molecular sieve and the mother liquor into a beaker, standing and layering the molecular sieve and the mother liquor, taking out 32mL of the mother liquor at the upper layer, adding the surfactant P1230.8g into the mixed suspension of the Y/SAPO-34/ZSM-11 molecular sieve and the mother liquor, stirring the mixture at 20 ℃ for 30min, adding the solution F, continuing stirring the mixture for 1h after the addition is finished, adding sulfuric acid into the stirred mixture, and adjusting the pH value of the system to 7. And finally, filtering and washing the obtained solid substance, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the mesoporous part is silicon-aluminum oxide, and the molar ratio of the silicon-aluminum oxide is 8.5: 1, the mesopores are regular mesopores, the aperture is 5nm, and the content of the Y molecular sieve is 62 wt%. The differential thermal failure temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1010 ℃, and the texture properties are shown in Table 1.
Example 2
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 28.7g of sodium hydroxide into 45.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 100g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the guiding agent. The molar ratio of each component of the guiding agent is as follows: 17Na2O:Al2O3:16SiO2:330H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the proportion of the aqueous solution is 1:0.5:7, dispersing 2g of SAPO-34 molecular sieve and 1g of ZSM-11 molecular sieve in 14g of aqueous solution of 6 wt% of potassium hydroxide and 5wt% of boric acid, heating to 70-80 ℃, stirring at constant temperature for 2h to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and adjusting the pH value of the slurry to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that in step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture to an autoclaveCrystallizing at 105 deg.c for 22 hr, and hydrothermal crystallizing to obtain Y/SAPO-34/ZSM-11 composite molecular sieve slurry E. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 7.5g of sodium hydroxide is dissolved in 58g of water, 9.2g of sodium metaaluminate is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved, so that a solution F is obtained. And (4) cooling the Y/SAPO-34/ZSM-11 molecular sieve obtained in the step (3) and the mother liquor to room temperature, transferring the molecular sieve and the mother liquor to a beaker, and adding P1231.6 g, 7.8g of water glass and the solution F in sequence at 25 ℃ while stirring. Stirring was continued for 2h at 25 ℃ and the nitric acid solution was added to the stirred mixture to finally bring the pH of the system to 8.5. And finally, filtering and washing the obtained solid substance, drying at 150 ℃ for 4h, and roasting at 450 ℃ for 10h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the mesoporous part is silicon-aluminum oxide, and the molar ratio of the silicon-aluminum oxide is 5:1, the mesopores are regular mesopores, the aperture is 8nm, and the content of the Y molecular sieve is 35 wt%. The differential thermal failure temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1008 ℃, and the texture properties are shown in Table 1.
Example 3
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 20.7g of sodium hydroxide into 45.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 93g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the directing agent. The molar ratio of each component of the guiding agent is as follows: 15Na2O:Al2O3:15SiO2:330H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the proportion of the aqueous solution is 1:0.75:3, 2g of SAPO-34 molecular sieve and 1.5g of ZSM-11 molecular sieve are dispersed in 6g of aqueous solution of 7 wt% of potassium hydroxide and 5wt% of boric acid, the aqueous solution is heated to 70-80 ℃, the aqueous solution is stirred for 2 hours at constant temperature to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and the pH value of the slurry is adjusted to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that in step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g of sodium hydroxide is dissolved in 27.6g of water, 16.1g of sodium metaaluminate is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved, so that a solution F is obtained. And (3) cooling the Y/SAPO-34/ZSM-11 molecular sieve and the mother liquor obtained in the step (3) to room temperature, taking out 90mL of the mother liquor, transferring the mixture of the residual mother liquor and the Y/SAPO-34/ZSM-11 molecular sieve into a beaker, adding 6.5g of CTAB and the solution F while stirring at 18 ℃, continuing stirring at 18 ℃ for 4 hours after the solution F is added, adding a hydrochloric acid solution into the stirred mixture, and adjusting the pH value of the system to 7.8. And finally, filtering and washing the obtained solid substance, drying at 110 ℃ for 32h, and roasting at 550 ℃ for 6h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the mesoporous part is silicon-aluminum oxide, and the molar ratio of the silicon-aluminum oxide is 4.5: 1, the mesopores are regular mesopores, the aperture is 5.5nm, and the content of the Y-type molecular sieve is 60 wt%. The differential thermal failure temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1020 ℃, and the texture properties are shown in Table 1.
Example 4
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 24.7g of sodium hydroxide into 30.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 107g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the directing agent. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:17SiO2:300H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the proportion of the aqueous solution is 1:0.5:5, 2g of SAPO-34 molecular sieve and 1g of ZSM-11 molecular sieve are dispersed in 10g of aqueous solution of 6 wt% of potassium hydroxide and 4wt% of boric acid, the aqueous solution is heated to 70-80 ℃, the aqueous solution is stirred for 2 hours at constant temperature to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and the pH value of the slurry is adjusted to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that in step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g of sodium hydroxide was dissolved in 37.6mL of water, and 4.4g of aluminum hydroxide was added thereto, followed by stirring until all the aluminum hydroxide was dissolved, to obtain solution F. And (3) filtering and washing the Y/SAPO-34/ZSM-11 molecular sieve containing the mother liquor obtained in the step (3) until the pH value of washing water is 9, adding water into the Y/SAPO-34/ZSM-11 molecular sieve for pulping, adding 4.8g of CTAB while stirring at the temperature of 20 ℃, stirring for 30min, then adding solution F and sulfuric acid, and adjusting the pH value of the system to be 8.0. And finally, filtering and washing the obtained mixture, drying at 125 ℃ for 16h, and roasting at 600 ℃ for 3h to obtain the Y/SAPO-34/ZSM-11/ASA composite material. Wherein the mesoporous part is silicon-aluminum oxide, and the molar ratio of the silicon-aluminum oxide is 5.5:1, the mesopores are regular mesopores, the aperture is 3.5nm, and the content of the Y-type molecular sieve is 60 wt%. The differential thermal failure temperature of NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1105 ℃, and the texture properties are shown in Table 1.
Example 5
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 24.7g of sodium hydroxide into 55.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 100g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the guiding agent. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:16SiO2:350H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the proportion of the aqueous solution is 1:0.5:7, dispersing 2g of SAPO-34 molecular sieve and 1g of ZSM-11 molecular sieve in 14g of aqueous solution of 8 wt% of potassium hydroxide and 5wt% of boric acid, heating to 70-80 ℃, stirring at constant temperature for 2h to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and adjusting the pH value of the slurry to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of Y/SAPO-34/ZSM-11 molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of guiding agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that of step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare the nano-composite materialTo obtain a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 99.6g of water glass was poured into 171.4mL of water to obtain solution F. And (3) filtering and washing the Y/SAPO-34/ZSM-11 molecular sieve containing the mother liquor obtained in the step (3) until the pH value of washing water is 9, adding water into the Y/SAPO-34/ZSM-11 molecular sieve for pulping, adding 3.8g of F127 and the solution F while stirring at the temperature of 20 ℃, and adjusting the pH value of the system to be 8.0 by using sulfuric acid. And finally, filtering and washing the obtained mixed substance, drying at 120 ℃ for 10h, and roasting at 550 ℃ for 5h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the molar ratio of silicon-aluminum oxide is 4.5: 1, the mesopores are regular mesopores, the aperture is 6.5nm, and the content of the Y-type molecular sieve is 65 wt%. The differential thermal destruction temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1008 ℃, and the texture properties are shown in Table 1.
Example 6
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 24.7g of sodium hydroxide into 45.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 100g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the guiding agent. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the proportion of the aqueous solution is 1:0.75:3, 2g of SAPO-34 molecular sieve and 1.5g of ZSM-11 molecular sieve are dispersed in 6g of aqueous solution of 8 wt% of potassium hydroxide and 5wt% of boric acid, the aqueous solution is heated to 70-80 ℃, the aqueous solution is stirred for 2 hours at constant temperature to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and the pH value of the slurry is adjusted to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of NaY type molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that in step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g of sodium hydroxide is dissolved in 27.6g of water, 4.4g of sodium metaaluminate is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved, so that a solution F is obtained. And (3) cooling the Y/SAPO-34/ZSM-11 molecular sieve and the mother liquor obtained in the step (3) to room temperature, taking out 180mL of the mother liquor, transferring the mixture of the residual mother liquor and the Y/SAPO-34/ZSM-11 molecular sieve to a plastic beaker, and adding P1231.3g, SAPO-34 and ZSM-11 molecular sieve slurry E, the solution D and sulfuric acid in sequence at 30 ℃ while stirring, wherein the pH value of the system is adjusted to 7.5. And finally, filtering and washing the obtained solid mixed substance, drying at 130 ℃ for 8h, and roasting at 650 ℃ for 4h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the mesoporous part is silicon-aluminum oxide, and the silicon-aluminum molar ratio of the silicon-aluminum oxide is 2.5: 1, the mesopores are regular mesopores, the aperture is 9.5nm, and the content of the Y-type molecular sieve is 80 wt% based on the Y/SAPO-34/ZSM-11/ASA composite material. The differential thermal failure temperature of NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1055 ℃, and the texture properties are shown in Table 1.
Example 7
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 24.7g of sodium hydroxide into 35.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 100g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the guiding agent. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:16SiO2:300H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the ratio of the aqueous solution is 1:1:7, dispersing 2g of SAPO-34 molecular sieve and 2g of ZSM-11 molecular sieve in 14g of aqueous solution of 9 wt% of potassium hydroxide and 4wt% of boric acid, heating to 70-80 ℃, stirring at constant temperature for 2h to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and adjusting the pH value of the slurry to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of NaY type molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that in step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g of sodium hydroxide is dissolved in 27.6g of water, 8.8g of sodium metaaluminate is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved, so that a solution F is obtained. And (3) cooling the Y/SAPO-34/ZSM-11 molecular sieve and the mother liquor obtained in the step (3) to room temperature, taking out 200mL of the mother liquor, transferring the mixture of the residual mother liquor and the Y/SAPO-34/ZSM-11 molecular sieve into a beaker, adding P1230.8g and F1274.2g while stirring at 25 ℃, stirring uniformly, then sequentially adding the solution F and sulfuric acid, and adjusting the pH value of the system to 8.0. And finally, filtering and washing the obtained solid substance, drying at 120 ℃ for 12h, and roasting at 550 ℃ for 4h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the mesoporous part is silicon-aluminum oxide, and the silicon-aluminum molar ratio of the silicon-aluminum oxide is 1.5: 1, the mesopores are regular mesopores, the aperture is 9.2nm, and the content of the Y-type molecular sieve is 80 wt% based on the Y/SAPO-34/ZSM-11/ASA composite material. The differential thermal destruction temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1027 ℃, and the texture properties are shown in Table 1.
Example 8
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 24.7g of sodium hydroxide into 45.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 100g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the guiding agent. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the proportion of the aqueous solution is 1:0.5:3, dispersing 2g of SAPO-34 molecular sieve and 1g of ZSM-11 molecular sieve in 6g of aqueous solution of 10wt% of potassium hydroxide and 2 wt% of boric acid, heating to 70-80 ℃, stirring at constant temperature for 2h to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and adjusting the pH value of the slurry to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of NaY type molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. 10.3g of directing agent, solution B and solutionAnd C, adding the slurry D and the water glass 75g (the specification is the same as that in the step 1) in sequence according to the preparation steps of the conventional NaY molecular sieve, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g of sodium hydroxide is dissolved in 27.6g of water, 8.8g of sodium metaaluminate is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved, so that a solution F is obtained. And (3) cooling the Y/SAPO-34/ZSM-11 molecular sieve and the mother liquor obtained in the step (3) to room temperature, taking out 220mL of the mother liquor, transferring the mixture of the residual mother liquor and the Y/SAPO-34/ZSM-11 molecular sieve into a beaker, adding P1231.2g and CTAB 3.8g at 25 ℃ while stirring, adding the solution F and sulfuric acid in sequence after uniformly stirring, and adjusting the pH value of the system to 8.0. And finally, filtering and washing the obtained solid substance, drying at 120 ℃ for 12h, and roasting at 550 ℃ for 4h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the mesoporous part is silicon-aluminum oxide, and the silicon-aluminum molar ratio of the silicon-aluminum oxide is 1:1, the mesopores are regular mesopores, the aperture is 7.5nm, and the content of the Y-type molecular sieve is 80 wt%. The differential thermal failure temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1034 ℃, and the texture properties are shown in Table 1.
Example 9
The sources of the raw materials were the same as in example 1, unless otherwise specified.
(1) Preparation of a guiding agent: adding 24.7g of sodium hydroxide into 55.9g of water, stirring until the sodium hydroxide is completely dissolved, adding 6.5g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a sodium metaaluminate solution A. And pouring 70g of the solution A and 100g of water glass into 65.5g of deionized water in sequence, stirring uniformly, and standing and aging at 30 ℃ for 22h to obtain the guiding agent. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:16SiO2:350H2O。
(2) Preparing SAPO-34 and ZSM-11 molecular sieve slurry: according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the ratio of the aqueous solution is 1:1:5, dispersing 2g of SAPO-34 molecular sieve and 2g of ZSM-11 molecular sieve in 10g of aqueous solution of 5wt% of potassium hydroxide and 5wt% of boric acid, heating to 70-80 ℃, stirring at constant temperature for 2h to obtain SAPO-34 and ZSM-11 molecular sieve slurry, and adjusting the pH value of the slurry to 7-8 to obtain SAPO-34 and ZSM-11 molecular sieve slurry D.
(3) Preparation of NaY type molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B, solution C and slurry D into 75g of water glass (the specification is the same as that in step 1) according to the conventional NaY molecular sieve preparation steps in sequence, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; transferring the reaction mixture into a high-pressure kettle, crystallizing at 105 ℃ for 22h, and obtaining Y/SAPO-34/ZSM-11 composite molecular sieve slurry E after hydrothermal crystallization is finished. Wherein the relative crystallinity of the NaY molecular sieve is 95 percent, the framework silicon-aluminum ratio is 5.2, the particle size is 200nm, and the differential thermal destruction temperature is 950 ℃.
(4) Preparation of Y/SAPO-34/ZSM-11/ASA composite material: 3.6g of sodium hydroxide is dissolved in 27.6g of water, 8.8g of sodium metaaluminate is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved, so that a solution F is obtained. And (3) cooling the Y/SAPO-34/ZSM-11 molecular sieve and the mother liquor obtained in the step (2) to room temperature, taking out 200mL of the mother liquor, transferring the mixture of the residual mother liquor and the Y/SAPO-34/ZSM-11 molecular sieve to a plastic beaker, adding 4.2g of CTAB and 4.2g of F1278.2 g of F1278 under stirring at 25 ℃, sequentially adding solution F and sulfuric acid, and adjusting the pH value of the system to 8.0. And finally, filtering and washing the obtained solid substance, drying at 120 ℃ for 12h, and roasting at 550 ℃ for 4h to obtain the Y/SAPO-34/ZSM-11/ASA composite material, wherein the mesoporous part is silicon-aluminum oxide, and the silicon-aluminum molar ratio of the silicon-aluminum oxide is 1.5: 1, the mesopores are regular mesopores, the aperture is 7.3nm, and the content of the Y-type molecular sieve is 70 wt%. The differential thermal destruction temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material is 1050 ℃, and the texture properties are shown in Table 1.
Comparative example 1
The conditions of example 1 were used, but P123 was not added in the preparation of the Y/ASA composite.
(1) Preparation of a guiding agent: adding 24.7g sodium hydroxide (analytically pure, Beijing chemical plant) into 45.9g water, stirring until sodium hydroxide is completely dissolved, adding 6.5g sodium metaaluminate (Shandong aluminum industry institute, Industrial product, Al)2O3Content 49.1 wt%), stirring until sodium metaaluminate is completely dissolved, and obtaining sodium metaaluminate solution A. 70g of solution A and 100g of water glass (Beijing Hongxing soda plant, SiO)2Content 27.81 wt%, Na2The O content is 8.74wt percent) is poured into 65.5g of deionized water in turn, and the guiding agent is obtained after standing and aging for 22h at 30 ℃ after even stirring. The molar ratio of each component of the guiding agent is as follows: 16Na2O:Al2O3:16SiO2:330H2O。
(2) Preparation of NaY type molecular sieve: 14.5g of aluminium sulphate was dissolved in 50.6g of water to form Al2O33.4 wt% of aluminum sulfate solution B; 4.5g of sodium hydroxide is dissolved in 50.4g of water, 10g of sodium metaaluminate (specification same as step 1) is added, and the mixture is stirred until the sodium metaaluminate is completely dissolved to form a sodium metaaluminate solution C. Adding 10.3g of directing agent, solution B and solution C into 75g of water glass (the specification is the same as that in step 1) in sequence according to the preparation steps of the conventional NaY molecular sieve, stirring uniformly, and then adding 48.5g of water to prepare a reaction mixture for synthesizing the NaY molecular sieve. The molar ratio of each component is 6.2Na2O:Al2O3:12SiO2:260H2O; the reaction mixture was transferred to an autoclave and crystallized at 105 ℃ for 22 h. And after the hydrothermal crystallization is finished, taking out the molecular sieve and the mother liquor, filtering, washing and drying to obtain the NaY type molecular sieve product.
The obtained NaY molecular sieve has a relative crystallinity of 95%, a framework silicon-aluminum ratio of 5.2, a particle size of 200nm, and a differential thermal failure temperature of 950 ℃.
(3) Preparation of Y/ASA composite material: the procedure of example 1 was repeated except that no surfactant was added thereto in the step (4). The aperture of the mesopores is 3.3-5.2 nm. The differential thermal failure temperature of NaY molecular sieve in the Y/ASA composite material is 910 ℃, and the texture properties are shown in Table 1.
Comparative example 2
A small-grained NaY molecular sieve was prepared and a Y/ASA composite was prepared as in example 1 of CN 1033503C.
(1) Preparation of a guiding agent: adding 29.5g of sodium hydroxide into 75g of water, stirring until the sodium hydroxide is completely dissolved, adding 4.78g of pseudo-boehmite, and stirring until the pseudo-boehmite is completely dissolved to obtain the sodium metaaluminate. Adding 200g of water glass into the prepared sodium metaaluminate and 12g of deionized water, mixing and stirring for 1h at 35 ℃, and then statically aging for 6h at 35 ℃ to obtain 16Na with molar ratio2O:Al2O3:15SiO2:320H2O, light transmittance<30% of a conventional directing agent.
189g of water glass with the specification same as that of the water glass is added into a conventional guiding agent, and after the water glass is placed at 30 ℃ for 1.5 hours, the light transmittance is 90 percent, and the molar composition is 20.6Na2O:Al2O3:30SiO2:495H2O clear and transparent solution of the improved directing agent, used after 24h at room temperature.
(2) Preparation of NaY type molecular sieve: according to the mol ratio of 3.84Na2O:Al2O3:12SiO2:220H2The synthetic formula of O is that 250g of water glass with the specification same as that of the water glass, 510g of the improved guiding agent prepared in the previous step and 160g of Al2O36.8% by weight of aluminum sulfate solution and 9.7g of sodium metaaluminate solution (Al)2O3Content 7.5 wt%, Na2The O content is 15wt percent), mixing and stirring for 1 hour, then heating to 97 ℃, crystallizing for 26 hours, filtering and drying.
The obtained NaY molecular sieve has relative crystallinity of 79%, framework Si/Al ratio of 5.8, particle size of 100nm, and differential thermal destruction temperature of 935 ℃.
(3) Preparation of Y/ASA composite material: same as in step (4) of example 4, CTAB was not added. The mesoporous part is silicon-aluminum oxide, the silicon-aluminum ratio is 5.5:1, the pore diameter of the mesoporous is 3.2-6.5 nm, the differential thermal failure temperature of a NaY molecular sieve in the Y/ASA composite material is 1050 ℃, and the texture properties are shown in Table 1.
Comparative example 3
Synthesizing NaY molecular sieve and preparing Y/ASA composite material according to the method provided by CN 201010514225.0.
(1) Synthesizing a guiding agent: taking 48g of water glass (the modulus is 3.0), adding 8g of polyethylene glycol PEG-2000, and stirring at the temperature of 15 ℃ at the stirring speed of 200 revolutions per minute for 1 hour to obtain a solution A; dissolving 7.8g of sodium hydroxide in 24mL of water, adding 1.6g of sodium metaaluminate, and stirring until the sodium metaaluminate is completely dissolved to obtain a solution B; stirring the solution A at a stirring speed of 3000 r/min, pouring the solution B into the solution A, continuously stirring at a stirring speed of 3000 r/min for 1.5h, finally stirring at a stirring speed of 200 r/min at 15 ℃ for aging for 12h, supplementing 20.4mL of water after aging, and continuously stirring at a stirring speed of 200 r/min at 15 ℃ for 0.5 h. The molar ratio of the other components except PEG-2000 is 18Na2O:Al2O3:22SiO2:426H2And O. Standing for 10 h.
(2) Synthesizing a NaY type molecular sieve: dissolving 3g of sodium hydroxide in 23.3mL of water, adding 3.7g of sodium metaaluminate, stirring until the sodium metaaluminate is completely dissolved, and adding 10.5g of polyethylene glycol 2000(PEG-2000) under stirring until the sodium metaaluminate is completely dissolved to obtain a solution C; 15g of aluminum sulfate was dissolved in 25mL of water to obtain solution D. Stirring the solution C at a stirring speed of 3000 r/min, and sequentially adding 90g of water glass solution, 10.6g of guiding agent, solution D and solution C to obtain sol E. The sol E was stirred at a stirring speed of 3000 rpm for 20 minutes at 15 ℃ and at a stirring speed of 200 rpm for 1 hour to give a colorless gel. Transferring the obtained colorless gel into a synthesis kettle with a polytetrafluoroethylene lining, and performing hydrothermal crystallization for 32 hours at 104 ℃ to obtain the NaY type molecular sieve.
The obtained nano NaY molecular sieve has the relative crystallinity of 82 percent, the framework silicon-aluminum ratio of 5.0, the particle size of 20-100 nm and the differential thermal destruction temperature of 900 ℃.
(3) Preparation of Y/ASA composite material: in the same manner as in step (4) of example 2, P123 was not added. The mesoporous part is silicon-aluminum oxide, the silicon-aluminum ratio is 5:1, the pore diameter of the mesoporous is 6.2-8.2 nm, the differential thermal failure temperature of a NaY molecular sieve in the Y/ASA composite material is 985 ℃, and the texture properties are shown in Table 1.
TABLE 1 texture Properties of NaY in Y/SAPO-34/ZSM-5/ASA composite
As can be seen from the results in Table 1, the differential thermal destruction temperature of the NaY molecular sieve in the Y/SAPO-34/ZSM-11/ASA composite material prepared by the method of the invention is improved. The Y/SAPO-34/ZSM-11/ASA composite material prepared by the invention has larger total pore volume and mesoporous pore volume, the average pore diameter of mesopores is 3-10 nm and is of a regular mesoporous structure, an open place is provided for organic macromolecule conversion, and the high-efficiency conversion of heavy oil molecules is facilitated. In the preparation process of the composite material, the mesoporous aperture of the composite material prepared without adding surface activity is randomly distributed.
Claims (9)
1. A preparation method of a Y/SAPO-34/ZSM-11/ASA hierarchical porous material comprises the following steps:
(1) preparing a guiding agent:
adding sodium hydroxide and an aluminum source into water, or adding the sodium hydroxide into the water until the sodium hydroxide is completely dissolved, and then adding the aluminum source to form a sodium metaaluminate solution A, wherein Al in the solution A2O32.5-10 wt% of Na2The content of O is 8-35 wt%; sequentially adding the solution A and the water glass solution into deionized water under stirring, uniformly stirring, and standing and aging at 15-50 ℃ for 0.5-60 h to prepare a guiding agent; the molar ratio of each component in the guiding agent is Na2O:Al2O3: SiO2: H2O=15~17:1:15~17:300~350；
(2) Preparation of slurry D:
according to SAPO-34 molecular sieve: ZSM-11 molecular sieve: the mass ratio of the water solution is 1: 0.5-1: 3-7, SAPO-34 and ZSM-11 molecular sieves are dispersed in the water solution, the water solution is heated to 70-80 ℃, stirred at a constant temperature for 2-5 hours, SAPO-34 and ZSM-11 molecular sieve slurry is obtained, and the pH values of the SAPO-34 and ZSM-11 molecular sieve slurry are adjusted, so that SAPO-34 and ZSM-11 molecular sieve slurry D is obtained;
the aqueous solution is an aqueous solution of 1-10 wt% of potassium hydroxide and 1-5 wt% of boric acid;
(3) preparing Y/SAPO-34/ZSM-11 composite molecular sieve slurry E:
dissolving an aluminum source in water to form Al2O31-4 wt% of solution B;
adding sodium hydroxide and an aluminum source into water, or adding the sodium hydroxide into the water until the sodium hydroxide is completely dissolved, and then adding the aluminum source to form a sodium metaaluminate solution C, wherein Al in the solution C2O3Is 3 to 9 wt% of Na2The content of O is 1-20 wt%;
adding the guiding agent, the solution B, the solution C and the slurry D into a water glass solution to prepare a reaction mixture for synthesizing the NaY molecular sieve; the addition amount of the guiding agent is 0.5-20 wt% based on 100wt% of the reaction mixture, and the molar ratio of each component of the reaction mixture for synthesizing NaY is as follows: na (Na)2O : Al2O3: SiO2:H2O=4~8:1:10~15:200~300；
Crystallizing the reaction mixture to obtain Y/SAPO-34/ZSM-11 composite molecular sieve slurry E;
(4) preparation of Y/SAPO-34/ZSM-11/ASA hierarchical pore material
Adding a surfactant into the Y/SAPO-34/ZSM-11 composite molecular sieve slurry E, adding an alkaline aluminum source or alkaline silicon source solution, adjusting the pH value of the system by using acid, and finally filtering, washing, drying and roasting the obtained solid mixed substance to obtain a Y/SAPO-34/ZSM-11/ASA hierarchical pore material;
wherein, in the step (4), the surfactant is at least one of CTAB, P123 and F127.
2. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the addition amount of the surfactant is 1-3 wt% of the weight of the Y/SAPO-34/ZSM-11/ASA hierarchical porous material.
3. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the pH value is 7-8.
4. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the pH value is 7-9.
5. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the crystallization conditions are as follows: crystallizing at 80-140 ℃ for 8-48 h.
6. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: in the steps (1) and (3), the aluminum source is one or more of sodium metaaluminate, pseudo-boehmite, aluminum nitrate, aluminum sulfate, aluminum hydroxide and gibbsite.
7. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the alkaline aluminum source is sodium metaaluminate or pseudo-boehmite, aluminum hydroxide or gibbsite dissolved in sodium hydroxide solution.
8. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the acid is sulfuric acid, hydrochloric acid or nitric acid.
9. The method for preparing Y/SAPO-34/ZSM-11/ASA hierarchical pore material as claimed in claim 1, wherein the method comprises the following steps: the mesopores in the Y/SAPO-34/ZSM-11/ASA hierarchical pore material are regular mesopores, the total pore volume is 0.52-0.62 mL/g, the micropore volume is 0.20-0.30 mL/g, and the mesopore volume is 0.27-0.40 mL/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710519563.5A CN109205636B (en) | 2017-06-29 | 2017-06-29 | Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710519563.5A CN109205636B (en) | 2017-06-29 | 2017-06-29 | Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109205636A CN109205636A (en) | 2019-01-15 |
| CN109205636B true CN109205636B (en) | 2020-02-14 |
Family
ID=64960895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710519563.5A Active CN109205636B (en) | 2017-06-29 | 2017-06-29 | Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109205636B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110368803B (en) * | 2019-07-22 | 2021-10-22 | 煤科集团沈阳研究院有限公司 | Gas absorbent and preparation method and application thereof |
| CN110642264B (en) * | 2019-11-11 | 2020-12-29 | 湘潭大学 | Synthesis method of nano needle-shaped ZSM-11 and mixed crystal molecular sieve thereof |
| CN114195165B (en) * | 2020-09-17 | 2023-08-22 | 中国石油天然气股份有限公司 | Composite carrier with step hole structure distribution and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007647A1 (en) * | 2002-07-12 | 2004-01-22 | Shell Internationale Research Maatschappij B.V. | Process to prepare a heavy and a light lubricating base oil |
| CN101205172A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Method for producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol |
| CN101269343A (en) * | 2007-03-23 | 2008-09-24 | 中国石油天然气股份有限公司 | Composite mesoporous molecular sieve hydrocracking catalyst and uses thereof |
| CN101632938A (en) * | 2008-07-24 | 2010-01-27 | 中国石油天然气股份有限公司 | Middle fraction oil type hydrocracking catalyst |
| WO2010102430A1 (en) * | 2009-03-10 | 2010-09-16 | 中国石油天然气股份有限公司 | Preparation method for increasing solid content of fcc catalyst |
| WO2011047528A1 (en) * | 2009-10-22 | 2011-04-28 | 中国石油天然气股份有限公司 | Bi-microporous-mesoporous composite molecular sieve y-beta/ mcm-41 and preparing method thereof |
| WO2011047527A1 (en) * | 2009-10-22 | 2011-04-28 | 中国石油天然气股份有限公司 | Double micro-mesoporous composite molecular sieve and preparation method thereof |
| CN102533316A (en) * | 2010-12-23 | 2012-07-04 | 中国石油天然气股份有限公司 | Method for selective hydrocracking of light oil |
| CN102553637A (en) * | 2010-12-17 | 2012-07-11 | 中国石油天然气股份有限公司 | Medium oil hydrocracking catalyst carrier and preparation and application thereof |
| CN102553638A (en) * | 2010-12-17 | 2012-07-11 | 中国石油天然气股份有限公司 | Double-microporous-mesoporous composite molecular sieve hydrocracking catalyst |
| CN103896299A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for synthesizing SAPO-31 molecular sieve nanocrystal from double templates |
| CN104707646A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院青岛生物能源与过程研究所 | Catalyst for toluene preparation through oxidative dehydrogenation of dimethyl ether, preparation method and applications thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6903674B2 (en) * | 2015-10-21 | 2021-07-14 | サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ | Cationic polymers and porous materials |
-
2017
- 2017-06-29 CN CN201710519563.5A patent/CN109205636B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007647A1 (en) * | 2002-07-12 | 2004-01-22 | Shell Internationale Research Maatschappij B.V. | Process to prepare a heavy and a light lubricating base oil |
| CN101205172A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Method for producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol |
| CN101269343A (en) * | 2007-03-23 | 2008-09-24 | 中国石油天然气股份有限公司 | Composite mesoporous molecular sieve hydrocracking catalyst and uses thereof |
| CN101632938A (en) * | 2008-07-24 | 2010-01-27 | 中国石油天然气股份有限公司 | Middle fraction oil type hydrocracking catalyst |
| WO2010102430A1 (en) * | 2009-03-10 | 2010-09-16 | 中国石油天然气股份有限公司 | Preparation method for increasing solid content of fcc catalyst |
| WO2011047528A1 (en) * | 2009-10-22 | 2011-04-28 | 中国石油天然气股份有限公司 | Bi-microporous-mesoporous composite molecular sieve y-beta/ mcm-41 and preparing method thereof |
| WO2011047527A1 (en) * | 2009-10-22 | 2011-04-28 | 中国石油天然气股份有限公司 | Double micro-mesoporous composite molecular sieve and preparation method thereof |
| CN102553637A (en) * | 2010-12-17 | 2012-07-11 | 中国石油天然气股份有限公司 | Medium oil hydrocracking catalyst carrier and preparation and application thereof |
| CN102553638A (en) * | 2010-12-17 | 2012-07-11 | 中国石油天然气股份有限公司 | Double-microporous-mesoporous composite molecular sieve hydrocracking catalyst |
| CN102533316A (en) * | 2010-12-23 | 2012-07-04 | 中国石油天然气股份有限公司 | Method for selective hydrocracking of light oil |
| CN103896299A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for synthesizing SAPO-31 molecular sieve nanocrystal from double templates |
| CN104707646A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院青岛生物能源与过程研究所 | Catalyst for toluene preparation through oxidative dehydrogenation of dimethyl ether, preparation method and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109205636A (en) | 2019-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5689890B2 (en) | Method for producing ZSM-5 zeolite using nanocrystalline ZSM-5 core | |
| KR101147007B1 (en) | Synthesis of BEA, MTW and MFI type zeolites possessing additional meso- and macro porosity using cyclicdiammonium organic templates | |
| CN107519933B (en) | Y/EU-1/SBA-15/ASA/MOF composite material and preparation method | |
| WO2011047528A1 (en) | Bi-microporous-mesoporous composite molecular sieve y-beta/ mcm-41 and preparing method thereof | |
| CN109205636B (en) | Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material | |
| CN102774855A (en) | Preparation method of microporous-mesoporous composite zeolite | |
| CN109304226B (en) | Hydrocracking catalyst for increasing production of heavy naphtha and aviation kerosene, and preparation method and application thereof | |
| CN105329912A (en) | Method for preparing meso-microporous composite Y molecular sieve | |
| CN113135578B (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN104646073B (en) | A kind of catalyst carrier for hydrgenating | |
| CN106268928A (en) | A kind of synthetic method of ordered big hole-mesoporous-micropore multi-stage porous catalyst | |
| CN109422274B (en) | Preparation method of hierarchical porous material | |
| CN107519927B (en) | Y/ZSM-22/SAPO-34/ASA/MOF composite material and preparation method | |
| Zhang et al. | Synthesis of hierarchical ZSM-5 composed of nanocrystals without a secondary template | |
| CN114425417B (en) | Naphtha catalytic cracking catalyst and preparation method and application thereof | |
| CN113086989B (en) | Preparation method of hierarchical pore NaY molecular sieve | |
| CN107519923B (en) | Y/EU-1/ZSM-5/ASA/ heteropoly acid composite material and preparation method | |
| US7968079B2 (en) | Ready-to-use seed composition and process thereof | |
| KR20080106806A (en) | Manufacturing method for mesoporous material with zeolite framework | |
| KR20220113825A (en) | DLM-1 molecular sieve, preparation method and use thereof | |
| CN107519938B (en) | Y/CeO2/ SBA-15/ASA/MOF composite material and preparation method | |
| CN107519925B (en) | Y/Sm2O3/ SBA-3/ASA composite material and preparation method | |
| CN107519921B (en) | Y/Sm2O3/ ZSM-22/ZSM-5/ASA composite material and preparation method | |
| CN112808296A (en) | Catalyst containing Y-type molecular sieve and preparation method thereof | |
| CN107519922B (en) | Y/Gd2O3/ ZSM-23/ZSM-5/ASA composite material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |