CN108654682A - It is a kind of to load the multistage pore canal composite material and preparation method for having TS-1 zeolite membranes - Google Patents
It is a kind of to load the multistage pore canal composite material and preparation method for having TS-1 zeolite membranes Download PDFInfo
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- CN108654682A CN108654682A CN201710205269.7A CN201710205269A CN108654682A CN 108654682 A CN108654682 A CN 108654682A CN 201710205269 A CN201710205269 A CN 201710205269A CN 108654682 A CN108654682 A CN 108654682A
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- zeolite
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- 239000010457 zeolite Substances 0.000 title claims abstract description 58
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 50
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000011148 porous material Substances 0.000 title claims abstract description 36
- 239000012528 membrane Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 230000000149 penetrating effect Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052594 sapphire Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- -1 alkyl carbon Chemical compound 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011240 wet gel Substances 0.000 claims description 3
- 238000003483 aging Methods 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000000887 hydrating effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
-
- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a kind of multistage pore canal composite materials for loading and having 1 zeolite membranes of TS, including α Al2O31 zeolite membrane of carrier and TS, the composite material are with 0.20~2 μm of macropore, the global formation material of mesoporous and 0.5~2nm the micropore of 2~10nm, and on the basis of composite material gross weight, 1 zeolite contents of TS are 4~15 weight %.Multistage pore canal composite material of the present invention is prepared using in-situ crystallization method, obtained load has the multistage pore canal composite material of 1 zeolite membranes of TS to have more uniform 1 zeolite membranes of TS and penetrating micron order macroporous structure, the limitation for overcoming material mass transfer during zeolite micropore reacts catalysis has very important significance to bulky molecular catalysis reaction.
Description
Technical field
The present invention relates to a kind of multistage pore canal composite material and preparation methods for loading and having TS-1 zeolite membranes.
Background technology
Zeolite molecular sieve refers to natural and artificial synthesized a kind of hydrosilicate, the structure and features with crystal, table
Face is solid skeletal, and internal micropore can play the role of binding molecule.The regular orderly, Kong Rong and Bi Biao in zeolite molecular sieve aperture
Area is larger, hydrothermal stability is good, be widely used in gas absorption and detach, ion exchange, fossil feedstock processing with refining,
The fields such as environmental protection, and act on and increasingly increasing.
Nineteen eighty-three, United States Patent (USP) USP4410501 first reported introduces the synthesis of pure silicon framework of molecular sieve by transition metals Ti
TS-1 molecular sieves.Since the molecular sieve analog is to H2O2, also there is unique adsorption activation performance even at a low concentration, it can be to more
Kind of organic compound carries out selective oxidation, as the hydroxylating of benzene and phenol, the epoxidation of alkene, the oximate of cyclohexanone, amine and
The reactions such as the oxidation of saturated alkane, attract wide attention.Moreover, TS-1 molecular sieve catalytics oxidation reaction condition is mild, selection
Property it is good, technical process is simple, reduzate is water, green non-pollution, to study highly selective hydrocarbon oxidization and exploitation
Friendly process is laid a good foundation.
But TS-1 molecular sieve pore passages narrow dimension (0.55nm), be unfavorable for macromolecule reactant or product transmission and
Diffusion, therefore its application is widely limited.The aperture of catalyst carrier used at present is still smaller, and between duct
Connectivity is bad, and reactants and products molecule is stayed by duct time lag, easy tos produce side reaction and carbon deposit, influences making for catalyst
Use the service life.Using being carrier with mesoporous and/or macroporous structure material, multistage pore canal is introduced in zeolite will break through TS-1 points
The limitation of son sieve micropore, can make the catalyst of preparation be widely used in oxidation reaction.
2006, Tong etc. was that the silica integral material with micron order through-hole is changed by transition template using charcoal
Multistage pore canal beta-zeolite (Y.C.Tong, the et al.Chem.Mater.18 (2006) 4218 of micro--Jie-macropore；
CN101003378).It utilizes all ducts of Carbon Materials filling gel integral post, obtains charcoal silicon compound, under certain condition
After unformed silica gel is converted into crystal form zeolite in charcoal silicon compound, Carbon Materials are flared off up to multistage pore canal beta-zeolite.
Zhao etc. is equally carrier using silica, and zeolite material in perforation type of multilevel pore canals is prepared for by vapor phase transport process
(CN101003377；CN101003380).Huang etc. used the Gel Precursor casting mold that silica is binder in 2010
NaP zeolites integral material (Y.Huang, the et al.Chem.Mater.22 with specific shape is prepared by vapor phase transport process
(2010) 5271), skeleton macropore reaches 3.5 μm.These large pore materials have through duct as carrier, to a certain extent
Mass-transfer efficiency is improved, but unformed hole wall makes hierarchical zeolite thermal stability, hydrothermal stability and the machinery of synthesis
Intensity is poor, and which also limits extensive uses.
In order to overcome drawbacks described above, Guan etc. to synthesize TS-1 molecules using in-situ crystallization method on honeycombed cordierite surface
It sieves (N.J.Guan, et al.Chem.Lett.29 (2000) 1084).Luo etc. reports whole in the porous SiSiC of biomorph
On ceramics ZSM-5 zeolite film (M.Luo, et al.J.Inorg.Mater.24 (2009) 330) is obtained using Situ Hydrothermal legal system.
High silicon was made by Direct Hydrothermal processing in coagulant liquid also by alumina support in 2010 by Tokudome etc. and low silicon boils
Stone (Y.Tokudome, et al.Microporous Mesoporous Mater.132 (2010) 538).Aluminium oxide has perforation
Type macropore can not only improve material mass transfer rate, while improve the thermal stability and mechanical strength of catalyst, anti-in catalysis
There is application potential in answering.
Crystallization liquid is added in sugar juice by Li Gang etc. (CN101962195A) obtains colloidal sol, it is thermally treated, pulverize,
Multi-stage porous titanium-silicon zeolite TS-1 is obtained after steam crystallization, washing, drying, roasting.Obtained hierarchical zeolite has tradition
The regular morphology and micropore canals of TS-1 also has mesoporous and macropore, is interconnected between duct.But what this method obtained
Zeolite is powder, and relative to global formation material, application range is very restricted.
Invention content
The object of the present invention is to provide a kind of multistage pore canal composite material for loading and having TS-1 zeolite membranes, which is
With macropore, mesoporous and micropore multi-stage artery structure global formation material, it is suitable for the catalysis reaction of macromolecular, pair can be reduced
Reaction and carbon deposit extend catalyst service life.
The present invention also provides the preparation methods that above-mentioned load has the multistage pore canal composite material of TS-1 zeolite membranes.
It is a kind of to load the multistage pore canal composite material for having TS-1 zeolite membranes, including α-Al2O3Carrier and TS-1 zeolite membranes, institute
It is the macropore with 0.20~2 μm to state composite material, the global formation material of mesoporous and 0.5~2nm the micropore of 2~10nm,
On the basis of composite material gross weight, zeolite content is 4~15%.
0.06~0.14cm of Kong Rongwei of the composite material3/ g, specific surface area are 60~190cm2/ g, with composite material
On the basis of gross weight, zeolite content is 4~15%, preferably 9~14%.
The XRD spectra of the composite material is to have TS-1 zeolites at 7.9 °, 8.8 °, 23.1 °, 23.6 ° and 24.4 ° at 2 angles θ
Characteristic peak occur.α-Al therein2O3Carrier, it is 0.20~2 μm to have penetrating pore passage structure, macropore diameter, mesoporous pore size
For 2~2nm.
It is 50~200nm that composite material of the present invention, which has more uniform TS-1 zeolite membranes, zeolite film thickness,.(scheme from SEM
In as can be seen that carrier on adhere to one layer of particulate matter, XRD characterization result prove particulate matter be TS-1 zeolites, particle it is big
Small is exactly the thickness of zeolite membrane.)
The preparation method provided by the invention for loading the multistage pore canal composite material for having TS-1 zeolite membranes, including following step
Suddenly：
(1) water, organic base, inorganic base are uniformly mixed, obtain alkali source；
(2) silicon source is added in alkali source, forms the solution after hydrolysis；
(3) titanium source is dissolved in hydrogen peroxide, is then added in the solution of step (2)；
(4) alcohol for generating system heating except dereaction, obtains crystallization liquid；
(5) by micron order through-hole α-Al2O3It is anti-to be placed in progress hydro-thermal in closed reactor in crystallization liquid for carrier impregnation
It answers.
(6) carrier is taken out and is washed, it is dry, roast the multistage pore canal composite material for there are TS-1 zeolite membranes to get load.
Specifically, the preparation method of multistage pore canal composite material provided by the invention can be implemented in the following manner：
In step (1), the alkali source is the mixed aqueous solution of organic base and inorganic base, and organic base is selected from tetramethyl hydroxide
Ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide or 4-propyl bromide, inorganic base are selected from sodium hydroxide or potassium hydroxide,
The molar ratio of material is organic base in alkali source：Water：Inorganic base=1：300~1000：0.6~5, preferably 1：600~850：1.8~
4。
In step (2), silicon source is slowly added into alkali source, 12~30h is hydrolyzed preferably at 10~40 DEG C.Wherein, institute
The silicon source stated is positive silicic acid tetraalkyl ester or trimethylethoxysilane, the alkyl carbon number in positive silicic acid tetraalkyl ester be C1~
One or more of C4, such as methyl orthosilicate, ethyl orthosilicate, butyl silicate, positive silicic acid tetra-isopropyl etc..
In step (3), preferably titanium source is slowly added into the aqueous solution of hydrogen peroxide, stirring is no less than 2h.Wherein titanium source
For tetralkyl titanate, alkyl carbon number therein is C1~C4, for example, tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate,
One or more of butyl titanate or tetrabutyl titanate etc..
In step (4), system is preferably warming up to 80~95 DEG C and removes 1~5h of alcohol, is optionally added water supplement loss
Quality, obtain crystallization liquid, it is spare to be down to room temperature.
In step (5), preferably under ultrasound or negative pressure, by micron order through-hole α-Al2O3Carrier impregnation 5 in crystallization liquid~
After 60min, carrier and crystallization liquid are placed in closed reactor, hydro-thermal reaction 1~3 day at 120~220 DEG C.
In step (6), preferably carrier is taken out and is washed, dry 12 at 110 DEG C~for 24 hours, in 400~700 DEG C of air
2~8h is roasted in atmosphere the multistage pore canal composite material of TS-1 zeolite membranes to get load.
Micron order through-hole α-Al described in step (5)2O3Carrier, it is 0.20~2 μm to have penetrating macropore, aperture.The load
Body is using aluminium chloride as silicon source, and water and ethyl alcohol are solvent, and (relative molecular weight is 1 × 10 to polyethylene oxide5~3 × 106) divide for phase
From agent, propylene oxide is gel inducing agents, and, dry and roasting aged by sol-gel method obtains；By controlling reactant
The addition of polyethylene oxide in material, water alcohol than etc. conditions the aperture of macropore is adjusted.
The micron order through-hole α-Al2O3Carrier can be prepared as follows：By polyethylene oxide, AlCl3·6H2O is dissolved in
Water and absolute ethyl alcohol in the mixed solvent are added propylene oxide, stir evenly, gained colloidal sol is sealed, and are aged, wet gel is through overdrying
Dry, roasting, obtains micron order through-hole α-Al2O3Integral material.Wherein, the dosage mass ratio of each reaction raw materials is polycyclic oxygen second
Alkane：AlCl3·6H2O：H2O：Ethyl alcohol：Propylene oxide=0.016~0.023：1：0.9~1.0：0.95~1.05：0.6~0.8.
The micron order through-hole α-Al2O3Carrier also can refer to Yasuaki Tokudome documents (Synthesis of
Monolithic Al2O3with Well-Defined Macropores and Mesostructured Skeletons via
The Sol-Gel Process Accompanied by Phase Separation, Chem.Mater.2007,19,3393-
3398.) prepare.
The XRD spectra of gained composite material of the invention is to have to spread out at 7.9 °, 8.8 °, 23.1 °, 23.6 ° and 24.4 ° at 2 angles θ
Penetrate peak appearance, this at five diffraction maximum be TS-1 zeolites characteristic peak, illustrate that the crystal form of obtained sample is TS-1 types.SEM figures are said
The presence (with 0.20~2 μm of macropore) of bright micron order macropore, N2Adsorption-desorption test chart illustrates mesoporous and micropore presence
(micropore of the mesoporous and average pore size 0.56nm with average pore size about 2.65nm).
Composite material provided by the invention makes the micron order through-hole skeleton structure of carrier be maintained, the TS-1 zeolites of load
Membrane structure is uniform, stablizes.The presence of micron order through-hole can shorten the diffusion length of reaction molecular, reduce the production of side reaction and carbon deposit
It is raw, so that product selectivity is easy to adjust and is controlled, and reduce the pressure drop of reaction unit to improve the processed in units efficiency of device；
Mesoporous presence can provide abundant inner ratio surface area and active site, this has the catalysis reaction of macromolecular very important
Meaning.
Compared with the carrier that existing synthesis TS-1 zeolite membranes use, synthetic method carrier provided by the invention is micron order
Through-hole α-Al2O3Integral material does not need forming processes, can carry out modulation to aperture by changing material ratio.Operating process letter
It is single, it is of less demanding to device, it is easily controllable, simple easily to repeat.
Description of the drawings
Fig. 1 is 1 gained micron order through-hole α-Al of the embodiment of the present invention2O3The scanning electron microscope sem figure of carrier A1；
Fig. 2 is the scanning electron microscope sem figure of 1 gained TS-1 zeolite samples A2 of comparative example；
Fig. 3 is the scanning electron microscope for the multistage pore canal composite A 3 that 3 gained load of the embodiment of the present invention has TS-1 zeolite membranes
SEM schemes；
Fig. 4 is micron order through-hole α-Al2O3Carrier A1, TS-1 zeolite sample A2 and load have the multi-stage porous of TS-1 zeolite membranes
The XRD spectra of road composite A 3.
Fig. 5 is the N for the multistage pore canal composite A 3 that load has TS-1 zeolite membranes2Adsorption-desorption figure.
Fig. 6 is the graph of pore diameter distribution for the multistage pore canal composite A 3 that load has TS-1 zeolite membranes.
Specific implementation mode
Below by embodiment, the invention will be further described, but the scope of the present invention is not only limited in as described below.
In embodiment raw material, polyethylene oxide is technical grade, and other is SILVER REAGENT.
In embodiment, XRD characterization uses 7000 type X-ray diffractometers of Japan Shimadzu Shimadzu XRD；SEM characterizations are adopted
With Hitachi, Japan HITACHI S-4800 type field emission scanning electron microscopes.
The relative amount of TS-1 zeolites carries out quantitative analysis by XRD spectra in multistage pore canal composite material.
The mechanical mixture that mass fraction containing TS-1 is 15%, 30%, 45%, 60%, 75%, 90% is first prepared respectively
TS-1/α-Al2O3, XRD analysis is carried out, using the diffracted intensity of its characteristic peak as x-axis, using its mass fraction as y-axis, workmanship
Make curve.The multistage pore canal composite material of synthesis is also subjected to XRD analysis, by being looked on its diffracted intensity to the working curve done
Go out its corresponding mass fraction, the mass fraction of TS-1 in composite material can be obtained.
Embodiment 1
The present embodiment is micron order through-hole α-Al2O3The preparation of integral material A1.
By 0.09g polyethylene oxide, 4.32g AlCl3·6H2O is dissolved in 4mL water and 4.35g absolute ethyl alcohol in the mixed solvents,
Stirring forms the uniform solution of water white transparency to being uniformly dissolved.3.11g propylene oxide is added under stirring and condition of ice bath, acutely
After stirring 5min, the mixture colloidal sol of gained is transferred in Teflon tube or glass tube.The seal of tube, 40 DEG C of ageings
For 24 hours, wet gel obtains micron order through-hole α-Al by dry, roasting2O3Integral material A1.
Comparative example 1
This comparative example is to prepare TS-1 zeolites according to a conventional method.
1.95g TPAOH are uniformly mixed with 22.34g water, with vigorous stirring slowly add the ethyl orthosilicate of 1.67g
Enter in system, continued hydrolysis is for 24 hours after mixing, under magnetic agitation.By 0.07g butyl titanates and 0.2g hydrogen peroxide be added to
In 5g water, after stirring 2h, obtained solution is slowly added dropwise into silicon source hydrating solution system, and after being added dropwise, stirring is no less than
30min.System is warming up to 85 DEG C, and heating 3h fully removes alcohol, and the quality of water supplement loss is added, and system is down to room temperature, is mixed
Close colloidal sol.Mixed sols is placed in closed stainless steel cauldron, hydro-thermal reaction 2d at 175 DEG C.It washes, be centrifugally separating to obtain powder
Crystallization product dries 12h at 110 DEG C, roasts 6h in 550 DEG C of air atmosphere, obtain TS-1 zeolite samples B1.
Embodiment 2
0.25g potassium hydroxide is dissolved in 20g water, 2.52g 4-propyl bromides are added and are uniformly mixed.Violent
The ethyl orthosilicate of 1.67g is slowly added in system under stirring, after mixing, continued hydrolysis 16h under magnetic agitation.It will
0.08g butyl titanates are added with 0.2g hydrogen peroxide into 8g water, after stirring 4h, are slowly added dropwise to silicon source hydrating solution system
In, after being added dropwise, stir 1h.System is warming up to 80 DEG C, and heating 5h fully removes alcohol, and the quality of water supplement loss, system is added
It is down to room temperature, obtains crystallization liquid.Under ultrasound or negative pressure, by micron order through-hole α-Al2O3Carrier impregnation 30min in crystallization liquid.
Then carrier and crystallization liquid are placed in closed stainless steel cauldron, hydro-thermal reaction 2d at 170 DEG C.Carrier is taken out and is washed, 110
Dry 12h, 6h is roasted in 550 DEG C of air atmosphere at DEG C, and obtaining load has the multistage pore canal composite material of TS-1 zeolite membranes
A2.On the basis of composite material gross weight, zeolite content 9%.
Embodiment 3
0.18g sodium hydroxides are dissolved in 22.34g water, 1.95g TPAOH are added and are uniformly mixed.Acutely stirring
Mix it is lower the ethyl orthosilicate of 1.67g is slowly added in system, continued hydrolysis is for 24 hours after mixing, under magnetic agitation.It will
0.07g butyl titanates are added with 0.2g hydrogen peroxide into 5g water, after stirring 2h, are slowly added dropwise to silicon source hydrating solution system
In, after being added dropwise, stirring is no less than 30min.System is warming up to 85 DEG C, and heating 3h fully removes alcohol, and water supplement loss is added
Quality, system are down to room temperature, obtain crystallization liquid.Under ultrasound or negative pressure, by micron order through-hole α-Al2O3Carrier impregnation is in crystallization
30min in liquid.Then carrier and crystallization liquid are placed in closed stainless steel cauldron, hydro-thermal reaction 2d at 175 DEG C.Carrier is taken out
Washing, dry 12h, 6h is roasted in 550 DEG C of air atmosphere at 110 DEG C, and obtaining load has the multi-stage porous of TS-1 zeolite membranes
Road composite A 3.On the basis of composite material gross weight, zeolite content 12%.
Claims (14)
1. a kind of loading the multistage pore canal composite material for having TS-1 zeolite membranes, including α-Al2O3Carrier and TS-1 zeolite membranes, it is described
Composite material is the macropore with 0.20~2 μm, the global formation material of mesoporous and 0.5~2nm the micropore of 2~10nm, with
On the basis of composite material gross weight, TS-1 zeolite contents are 4~15 weight %.
2. composite material described in accordance with the claim 1, wherein it is 0.06~0.14cm that the composite material hole, which holds,3/ g, specific surface
Product is 60~190cm2/g。
3. composite material described in accordance with the claim 1 the, wherein α-Al2O3Carrier has penetrating pore passage structure, macropore
Aperture is 0.20~2 μm, and mesoporous pore size is 2~5nm.
4. a kind of preparation method loading the multistage pore canal composite material for having TS-1 zeolite membranes, comprises the steps of：
(1) water, organic base, inorganic base are uniformly mixed, obtain alkali source；
(2) silicon source is added in alkali source, forms the solution after hydrolysis；
(3) titanium source is dissolved in hydrogen peroxide, is then added in the solution of step (2)；
(4) alcohol for generating system heating except dereaction, obtains crystallization liquid；
(5) by micron order through-hole α-Al2O3Carrier impregnation is placed in closed reactor in crystallization liquid and carries out hydro-thermal reaction；
(6) carrier is taken out and is washed, it is dry, roast the multistage pore canal composite material for there are TS-1 zeolite membranes to get load.
5. preparation method according to claim 4, wherein in step (1), the alkali source is the mixed of organic base and inorganic base
Heshui solution.
6. preparation method according to claim 5, wherein organic base is selected from tetramethylammonium hydroxide, tetraethyl hydroxide
Ammonium, tetrapropylammonium hydroxide or 4-propyl bromide and/or inorganic base are selected from sodium hydroxide or potassium hydroxide and/or alkali source
The molar ratio of material is organic base：Water：Inorganic base=1：300~1000：0.6~5.
7. preparation method according to claim 4, wherein silicon source described in step (2) be positive silicic acid tetraalkyl ester or
Trimethylethoxysilane, the alkyl carbon number in positive silicic acid tetraalkyl ester are C1~C4.
8. preparation method according to claim 4, wherein the titanium source described in step (3) is tetralkyl titanate, wherein
Alkyl carbon number be C1~C4.
9. preparation method according to claim 4, wherein in step (4), by system be warming up to 80~95 DEG C except alcohol 1~
5h。
10. preparation method according to claim 4, wherein in step (5), under ultrasound or negative pressure, by micron order through-hole
α-Al2O3Carrier impregnation is placed in closed reactor in crystallization liquid after 5~60min, by carrier and crystallization liquid, at 120~220 DEG C
Hydro-thermal reaction 1~3 day.
11. preparation method according to claim 4, wherein in step (6), after carrier is washed dry 12 at 110 DEG C
~for 24 hours, 2~8h is roasted in 400~700 DEG C of air atmosphere.
12. preparation method according to claim 4, wherein the micron order through-hole α-Al2O3Carrier is made by the following method
It is standby：By polyethylene oxide, AlCl3·6H2O is dissolved in water and absolute ethyl alcohol in the mixed solvent, and propylene oxide is added, stirs evenly, will
Gained colloidal sol seals, ageing, and wet gel obtains micron order through-hole α-Al by dry, roasting2O3Integral material.
13. preparation method according to claim 12, wherein the dosage mass ratio of each reaction raw materials is polyethylene oxide：
AlCl3·6H2O：H2O：Ethyl alcohol：Propylene oxide=0.016~0.023：1：0.9~1.0：0.95~1.05：0.6~0.8.
14. the load that one of claim 4-13 the methods obtain has the multistage pore canal composite material of TS-1 zeolite membranes.
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