CN106512752A - Method for preparing b-axial oriented ZSM-5 molecular sieve nano-ceramic composite membrane - Google Patents
Method for preparing b-axial oriented ZSM-5 molecular sieve nano-ceramic composite membrane Download PDFInfo
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- CN106512752A CN106512752A CN201611100750.1A CN201611100750A CN106512752A CN 106512752 A CN106512752 A CN 106512752A CN 201611100750 A CN201611100750 A CN 201611100750A CN 106512752 A CN106512752 A CN 106512752A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 109
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 239000000919 ceramic Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 44
- 239000010703 silicon Substances 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229920001661 Chitosan Polymers 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000009415 formwork Methods 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- 238000001548 drop coating Methods 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 36
- 239000000499 gel Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 19
- 230000007547 defect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000003760 hair shine Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 under stirring Chemical compound 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 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
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a method for preparing a b-axial oriented ZSM-5 molecular sieve nano-ceramic composite membrane. The method comprises the following steps: (1) preparing ZSM-5 molecular sieve synthetic liquid by using an aluminum source, a silicon source, an organic template agent and water as raw materials, and reacting the synthetic liquid to obtain a ZSM-5 molecular sieve seed crystal; (2) dissolving the aluminum source in distilled water to prepare alumina sol, heating the alumina sol to 80-95 DEG C, and adding chitosan and dissolving; and (3) adding the ZSM-5 molecular sieve seed crystal into the mixed solution, coating the mixed solution on the outer surface of a carrier, putting the carrier into a heating device, heating to 480-800 DEG C, and keeping temperature constant to obtain the b-axial oriented ZSM-5 molecular sieve nano-ceramic composite membrane. The preparation process is mild in condition and simple in operation, can be used for developing a novel composite membrane, and is beneficial to industrialization of gas separation, purification, alcohol-water low-energy-consumption membrane separation and other technologies by combining the advantages of the oriented ZSM-5 molecular sieve membrane and a nano-ceramic membrane.
Description
Technical field
The invention belongs to inorganic porous material, UF membrane and membrane catalytic technology field, and in particular to a kind of b- axles orientation
ZSM-5 molecular sieve nano ceramics is combined membrane preparation method.
Background technology
ZSM-5 is the wider zeolite molecular sieve of a class range of application, and it has two-dimensional channel structure, and its effective aperture is about
0.55nm, is suitable for the various essential industry raw materials of adsorbing separation, and has good shape selective catalysis performance；And it is higher due to having
Silica alumina ratio (Si/Al ratio), its hydrothermal stability and chemical stability it is preferable.Therefore, type ZSM 5 molecular sieve film is to be recognized
For the molecular screen membrane of most potentiality to be exploited.Pure silicon or high silica ZSM-5 type (silicalite-1) molecular screen membrane, its not only stability
It is very high, and there is good hydrophobic property, efficiently separating for water and organic matter, quilt can be realized by Preferential adsorption organic matter
It is widely used in the purification of low-concentration ethanol zymotic fluid, there is in terms of fuel ethanol production very high industrial application value.Contain
Transition metal hetero-atom type ZSM 5 molecular sieve film, the transition metal in its duct can play good shape selective catalysis performance, table
Reveal special redox active, many redox reactions can be catalyzed.As hetero atom type ZSM 5 molecular sieve film has
Dual-use function is separated and is catalyzed, it not only can be improved by selectively removing a certain component in product by balance limit
The reaction conversion ratio of system and selectivity, also allow in same reactor while carrying out two to react, make the product of first reaction
Thing selectively passes through film and participates in second reaction, realizes catalysis and detached combination, thus in membrane reactor and micro-
Type reactor has huge application prospect in field.
In recent years, type ZSM 5 molecular sieve film is at aspects such as UF membrane, Membrane catalysis, chemical sensor and microelectronic components
Using more and more wider.The experimental results show, micro-structural and the crystal orientation of zeolite molecular sieve film directly affect its separate with
Catalytic performance.As the type ZSM 5 molecular sieve intracrystalline pore road structure of different orientation differs greatly, type ZSM 5 molecular sieve film
Orientation can have a strong impact on its mass transfer and characteristic electron, and then which is separated and catalytic performance produces tremendous influence.So, closely
The preparation of ZSM-5 type orientation molecular sieve membranes over year is increasingly paid close attention to by people.Although in the nearly more than ten years, the system of molecular screen membrane
Standby technique has obtained rapid development, but due to the restriction of the aspects such as carrier flatness, type ZSM 5 molecular sieve film preparation with
Application aspect also there are problems that many insoluble.
The content of the invention
It is an object of the invention to provide a kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axles orientation,
The preparation method overcomes the technical bottleneck in existing ZSM-5 molecular sieve film preparation technique, and its process conditions is gentle, process it is simple and
Novel composite membrane with low cost, preparing, combines the advantage of orientation ZSM-5 molecular sieve film and nano ceramics film, while more
Be conducive to the technological industrializations such as gas separation, purification and the separation of alcohol water low-power membrane.
In order to realize foregoing invention purpose, technical scheme is as follows：
It is an object of the invention to provide a kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axles orientation, bag
Include following steps：
(1) preparation of ZSM-5 molecular sieve crystal seed：With silicon source, silicon source, organic formwork agent and water as raw material, reaction system
Feed molar composition is calculated as with oxide：1Al2O3:aSiO2:bTemplate:cH2O, a=10～1000, b=0.5～3, c=
4.5～100, Template are organic formwork agent, according to above-mentioned consumption, silicon source are added to the water, and are stirred to being completely dissolved into
For Ludox, under stirring, silicon source and organic formwork agent are progressively added drop-wise in Ludox successively, and are continued stirring until
It is even, the pH of reactant liquor is adjusted to into 11～12, that is, ZSM-5 molecular sieve Synthesis liquid is obtained；
The ZSM-5 molecular sieve Synthesis liquid is put in reaction vessel, then reaction vessel is put into and has been warming up to
Heat in 140 DEG C～200 DEG C of heater, and react 12～100h under agitation, after completion of the reaction, reaction vessel is certainly
Room temperature is so cooled to, ZSM-5 molecular sieve sample is then taken out, is cleaned and is dried, obtain ZSM-5 molecular sieve crystal seed；
(2) preparation of Alumina gel：Organic silicon source or inorganic silicon source are dissolved in distilled water and make Alumina gel, in Alumina gel
Aluminium ion mass concentration is 0.01～0.5g/ml；The Alumina gel solution temperature is risen to into 80 DEG C～95 DEG C, in stirring
Under, add shitosan dissolving so that the chitosan mass concentration in solution is 0.005～0.1g/ml, and will be the mixed solution cold
But to room temperature；
(3) step (1) is obtained the ZSM-5 molecular sieve crystal seed to be added in step (2) mixed solution, it is described
ZSM-5 molecular sieve crystal seed is 0.01～1 with the mol ratio of silicon source in the mixed solution；Will containing ZSM-5 molecular sieve crystal seed and
The mixed solution of Alumina gel is coated on carrier outer surface using spin-coating method or drop-coating, and then carrier is put in heater,
With 0.01～1m3The constant flow rate of/h is passed through air or oxygen, rises to 480 DEG C～800 DEG C with 10 DEG C/min heating rates, and permanent
5～10h of temperature, prepares the ZSM-5 molecular sieve nano ceramics composite membrane of b- axles orientation.
In the application, the room temperature of indication is 20 DEG C～28 DEG C.The effect of shitosan is to make nano ceramics film and ZSM-5 molecules
Sieve crystal can preferably with reference in carrier surface.
The application can prepare the ZSM-5 molecular sieve nano ceramics of densification on macropore ceramics or stainless steel carrier and be combined
Film, and by adjusting composition, Hydrothermal Synthesiss temperature and the synthesis such as the applying structure guiding agent-shitosan bar on carrier of Synthesis liquid
Part, promotes molecular sieve crystal oriented growth, while the purpose for adjusting film thickness is can reach, it is final directly to prepare on macropore carrier
Go out complete orientation ZSM-5 molecular sieve nano ceramics composite membrane, the completeness of ZSM-5 molecular sieve film can be improved, and can be effectively
Reduce production cost.
Preferably, the silicon source described in step (1) is selected from sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or contains 2
One kind in the aluminium alcoholates of～4 carbon atoms, described organic formwork agent are selected from TPAOH, 4-propyl bromide or three
One kind in ethamine, described silicon source are selected from the one kind in tetraethyl orthosilicate, Ludox, silicic acid or waterglass.
Preferably, the organic silicon source described in step (2) is aluminium isopropoxide, and described inorganic silicon source is aluminium chloride or sulfuric acid
Aluminium.
Preferably, described carrier is the ceramics of porous stainless steel or sheet.
Preferably, the mixed solution containing ZSM-5 molecular sieve crystal seed and Alumina gel described in step (3) adopt spin-coating method or
Drop-coating is coated on vector outside, and coating thickness is 5～10 μm.
The invention has the beneficial effects as follows：
(1) by the change of the synthesis conditions such as material formula, the thickness of nano ceramics film can be regulated and controled, and film
Completeness is high；
(2) the ZSM-5 molecular sieve film for specific b axles orientation prepared by, the process conditions of the present invention are gentle, operation more
Simply, cost is more cheap, applicability is more extensive, the Novel composite membrane developed, and combines orientation ZSM-5 molecular sieve film and receives
The advantage of rice ceramic membrane, while being more beneficial for the technological industrializations such as gas separation, purification and the separation of alcohol water low-power membrane.
Description of the drawings
Fig. 1 is the ceramic monolith employed in the present invention and is coated with the nanometer α-Al of different-thickness2O3The SEM of film shines
Piece：A () is not modified ceramic monolith plane SEM photograph；(b) adopt concentration for 0.01g/ml Alumina gels prepare nanometer α-
Al2O3Thin film planar SEM photograph；C () adopts concentration for the nanometer α-Al of 0.5g/ml Alumina gels preparation2O3Thin film planar SEM shines
Piece；D () adopts concentration for the nanometer α-Al of 0.01g/ml Alumina gels preparation2O3Thin-membrane section SEM photograph；(e) adopt concentration for
Nanometer α-Al prepared by 0.5g/ml Alumina gels2O3Thin-membrane section SEM photograph；
Fig. 2 is ZSM-5 molecular sieve nano ceramics composite membrane SEM photograph prepared in the embodiment of the present invention 1；
Fig. 3 is ZSM-5 molecular sieve nano ceramics composite membrane SEM photograph prepared in the embodiment of the present invention 2；
Fig. 4 is ZSM-5 molecular sieve nano ceramics composite membrane SEM photograph prepared in the embodiment of the present invention 3；
Fig. 5 is ZSM-5 molecular sieve nano ceramics composite membrane SEM photograph prepared in the embodiment of the present invention 4；
Fig. 6 is ZSM-5 molecular sieve nano ceramics composite membrane SEM photograph prepared in the embodiment of the present invention 5；
Equipment schematic diagrames of the Fig. 7 for single-component gas permeability test.
Specific embodiment
With reference to instantiation, the present invention is further elucidated.It should be understood that these embodiments are merely to illustrate this
It is bright, rather than limit protection scope of the present invention.Technical staff is made according to the present invention in actual applications improvement and tune
It is whole, still fall within protection scope of the present invention.
The equipment used except special instruction, the present invention and reagent are the art routine commercial products.
A kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axles orientation, comprises the steps：
(1) preparation of ZSM-5 molecular sieve crystal seed：With silicon source, silicon source, organic formwork agent and water as raw material, reaction system
Feed molar composition is calculated as with oxide：1Al2O3:aSiO2:bTemplate:cH2O, a=10～1000, b=0.5～3, c=
4.5～100, Template are organic formwork agent, according to above-mentioned consumption, silicon source are added to the water, and are stirred to being completely dissolved into
For Ludox, under stirring, silicon source and organic formwork agent are progressively added drop-wise in Ludox successively, and are continued stirring until
It is even, the pH of reactant liquor is adjusted to into 11～12, that is, ZSM-5 molecular sieve Synthesis liquid is obtained；
The ZSM-5 molecular sieve Synthesis liquid is put in reaction vessel, then reaction vessel is put into and has been warming up to
Heat in 140 DEG C～200 DEG C of heater, and react 12～100h under agitation, after completion of the reaction, reaction vessel is certainly
Room temperature is so cooled to, ZSM-5 molecular sieve sample is then taken out, is cleaned and is dried, obtain ZSM-5 molecular sieve crystal seed；
(2) preparation of Alumina gel：Organic silicon source or inorganic silicon source are dissolved in distilled water and make Alumina gel, in Alumina gel
Aluminium ion mass concentration is 0.01～0.5g/ml；The Alumina gel solution temperature is risen to into 80 DEG C～95 DEG C, in stirring
Under, add shitosan dissolving so that the chitosan mass concentration in solution is 0.005～0.1g/ml, and will be the mixed solution cold
But to room temperature；
(3) step (1) is obtained the ZSM-5 molecular sieve crystal seed to be added in step (2) mixed solution, it is described
ZSM-5 molecular sieve crystal seed is 0.01～1 with the mol ratio of silicon source in the mixed solution；Will containing ZSM-5 molecular sieve crystal seed and
The mixed solution of Alumina gel is coated on carrier outer surface using spin-coating method or drop-coating, and then carrier is put in heater,
With 0.01～1m3The constant flow rate of/h is passed through air or oxygen, rises to 480 DEG C～800 DEG C with 10 DEG C/min heating rates, and permanent
5～10h of temperature, prepares the ZSM-5 molecular sieve nano ceramics composite membrane of b- axles orientation.
Silicon source in the aluminium alcoholates of sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or 2～4 carbon atoms one
Kind, its preferred aluminium isopropoxide and boehmite.Organic formwork agent is selected from TPAOH (TPAOH), tetrapropyl bromination
One kind in ammonium (TPABr) or triethylamine (TEA).Silicon source in tetraethyl orthosilicate, Ludox, silicic acid or waterglass one
Kind.
The following is and the present invention is further illustrated, but content not thereby limiting the invention.
The compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of the b- axles orientation of the embodiment explanation present invention.
Embodiment 1
(1) preparation of ZSM-5 molecular sieve crystal seed
According to 1Al2O3:1000SiO2:3TEA:100H2The material proportion of O prepares Synthesis liquid.Silicon source and silicon source in reaction
That what is be respectively adopted is AlCl3And tetraethyl orthosilicate, while adopting triethylamine for template.Add in pure water a certain amount of
NaOH so that the pH value of solution dissolves tetraethyl orthosilicate 5h 11～12, under stirring condition so as to complete hydrolysis；Treat the aqueous solution
The AlCl of proportional quantity is added after clarification3, stirring and dissolving 3h, after the dissolving completely of each material, adjust the pH value of reactant liquor 11～
12, and aging 10h at room temperature, in then adding reactor.Reactor is placed in and has been warming up in 140 DEG C of baking oven, and
100h is reacted in stirring condition, after completion of the reaction, reactor is naturally cooling to room temperature, then take out ZSM-5 molecular sieve sample, and
Cleaned with distilled water, be dried to obtain ZSM-5 molecular sieve crystal seed.
(2) preparation of Alumina gel
Under agitation, aluminium isopropoxide is made an addition in distilled water, in making solution, aluminium ion mass concentration is 0.5g/
Ml, and the nitric acid that 0.5g concentration is 98% is added dropwise so that solution ph is 2, and persistently stirs 2h, in addition reactor simultaneously then
Reactor is placed in and has been warming up in 150 DEG C of baking oven；
Prepared Alumina gel solution is warming up to into 95 DEG C, then under agitation, shitosan dissolving is added so that molten
Chitosan concentration in liquid is 0.1g/ml, when shitosan is completely dissolved in homogeneous state, mixed solution is cooled to room temperature.
(3) preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axles orientation
Under agitation, step (1) is obtained into ZSM-5 molecular sieve crystal seed and is added to mixing prepared in step (2)
In solution, the addition of ZSM-5 molecular sieve crystal seed and mixed solution presses molar ratio of material ZSM-5:Al2O3=1:1, and persistently stir
Mix 5h so as to become homogeneous mixed liquor；
Using drop-coating, prepared homogeneous mixed liquor is coated on into ceramic monolith outer surface, coating thickness is 5 μm, and
Afterwards the carrier after coating is put in temperature programmed control atmosphere furnace, with 0.01m3The constant flow rate of/h is passed through air or oxygen, with 10
DEG C/min heating rates rise to 800 DEG C, and constant temperature 10h, make Alumina gel fully oxidized, prepare the individual layer ZSM-5 of b- axles orientation
Molecular sieve nano ceramics composite membrane.
SEM detections are carried out to the ZSM-5 molecular sieve nano ceramics composite membrane prepared by embodiment 1, its result such as Fig. 2 institutes
Show, prepared ZSM-5 molecular sieve film layer flatness is higher, no significant defect, molecular sieve particle diameter is 0.5 μm.
Embodiment 2
(1) preparation of ZSM-5 molecular sieve crystal seed
It is substantially the same manner as Example 1, different be prepare ZSM-5 molecular sieve Synthesis liquid during, the aluminium for being adopted
Source and silicon source are respectively boehmite and waterglass, and adopt 4-propyl bromide for template.
(2) preparation of Alumina gel
Essentially identical with implementing 1, different is as silicon source using aluminum sulfate.
(3) preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axles orientation
Substantially the same manner as Example 1, different is that adopted carrier is porous stainless steel, and air velocity is changed into 1m3/
H, calcining heat are changed into 480 DEG C.
SEM detections are carried out to the ZSM-5 molecular sieve nano ceramics composite membrane prepared by embodiment 2, its result such as Fig. 3 institutes
Show, prepared ZSM-5 molecular sieve film layer flatness is higher, no significant defect, molecular sieve particle diameter is 0.4 μm.
Embodiment 3
(1) preparation of ZSM-5 molecular sieve crystal seed
It is substantially the same manner as Example 1, different be prepare ZSM-5 molecular sieve Synthesis liquid during, the aluminium for being adopted
Source and silicon source difference sodium aluminate and Ludox, template use TPAOH.Meanwhile, the material formula of Synthesis liquid
For 1Al2O3:10SiO2:0.5TPAOH:4.5H2O, reaction temperature are set as 200 DEG C, and the reaction time is 12h.
(2) preparation of Alumina gel
It is substantially the same manner as Example 1, different be using aluminium chloride as silicon source, and with and adjust silicon source addition,
Aluminium ion mass concentration in solution is made to be 0.01g/ml, Alumina gel is warming up to 80 DEG C；Have adjusted shitosan addition so that solution
In chitosan concentration be 0.005g/ml.
(3) preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axles orientation
Substantially the same manner as Example 1, different is the addition that have adjusted ZSM-5 molecular sieve so that molar ratio of material
ZSM-5:Al2O3For 0.01:1；Mixed solution is coated carrier surface by spin-coating method, and coating thickness is 10 μm, and using the speed that heats up
Muffle furnace is warming up to 800 DEG C for 10 DEG C/min by rate, and calcines 5h at this temperature.
SEM detections are carried out to the ZSM-5 molecular sieve nano ceramics composite membrane prepared by embodiment 3, its result such as Fig. 4 institutes
Show, prepared ZSM-5 molecular sieve film layer flatness is higher, no significant defect, molecular sieve particle diameter is 2.5 μm.
Embodiment 4
ZSM-5 molecular sieve nano ceramics composite membrane, ZSM-5 molecular sieve Synthesis liquid proportioning are prepared using Vacuum-assisted method method
And it is same as Example 1 with synthesis liquid preparing process.Different is used silicon source for aluminium isopropoxide, and be by without
The ceramic monolith of modification reacts 100h in being directly placed into Synthesis liquid, prepares ZSM-5 molecular sieve nano ceramics composite membrane.Its result
As shown in figure 5, as carrier surface is not modified, there is larger defect thereon, prepared ZSM-5 molecular sieve film is caused to have
Local location subsides, and defect is obvious.
Embodiment 5
(1) preparation of ZSM-5 molecular sieve
ZSM-5 molecular sieve Synthesis liquid matches somebody with somebody when same as Example 1 with synthesis liquid preparing process, and different is to be used
Silicon source be aluminum sulfate.
(2) preparation of ZSM-5 molecular sieve ceramic membrane
ZSM-5 molecular sieve nano ceramics composite membrane is prepared using secondary growth method, directly by prepared ZSM-5 molecular sieve
Crystal seed is spun on not modified ceramic monolith surface；The ceramic monolith for being supported with molecular sieve seed is put into into ZSM-5 point then
In son sieve Synthesis liquid, synthesis formula of liquid and preparation process are same as Example 1.
Its result is as shown in fig. 6, as carrier surface defect is more obvious, cause prepared ZSM-5 molecular sieve film table
Face is rough and uneven in surface, and some areas have ceramic matrix to expose, and defect is more obvious.
Fig. 1 is the ceramic monolith employed in the present invention and is coated with the nanometer α-Al of different-thickness2O3The SEM of film shines
Piece：A () is not modified ceramic monolith plane SEM photograph；(b) adopt concentration for 0.01g/ml Alumina gels prepare nanometer α-
Al2O3Thin film planar SEM photograph；C () adopts concentration for the nanometer α-Al of 0.5g/ml Alumina gels preparation2O3Thin film planar SEM shines
Piece；D () adopts concentration for the nanometer α-Al of 0.01g/ml Alumina gels preparation2O3Thin-membrane section SEM photograph；(e) adopt concentration for
Nanometer α-Al prepared by 0.5g/ml Alumina gels2O3Thin-membrane section SEM photograph.
From figure (a), the ceramic monolith surface relief modified without Alumina gel is uneven, and between carrier surface particulate matter
Cohesive force is weaker.From figure (b)～(e), as coating nanometer α-Al2O3After film, the flatness of carrier surface has and significantly changes
It is apt to, and the flatness on surface strengthens with the increase of Alumina gel concentration.Meanwhile, nanometer α-Al2O3The thickness of film is also with Alumina gel
The increase of concentration and increase (when Alumina gel concentration is improved to 0.5g/ml by 0.01g/ml, nanometer α-Al2O3Film thickness is by 5 μ
M increases to 10 μm).
The detection of the ZSM-5 molecular sieve nano ceramics composite membrane completeness of b- axles orientation
The application using one-component gas permeating method (Applied Surface Science, 2008,254:2353-
2358) completeness of the composite molecular sieve film for (testing leakage method) synthesized by detection, its flow process are as shown in Figure 7.Removed template method it
Before, the complete molecular screen membrane being synthesized is air-locked；If synthesized molecular screen membrane is defective, gas is then permeable
's.Test in leakage method experiment, in feed end N2Gas is permeating end H as spike gas2Gas is permeated by determining as purge gass
The N at end2Gas content, you can judge the completeness of molecular screen membrane.Test in leakage method experiment, membrane cisterna temperature constant at 25 DEG C, front end N2Gas
Pressure is 0.5MPa, rear end H2Gas is normal pressure, and rear end gas velocity is about 10ml/min, and backend gas are directly entered gas-chromatography,
N in on-line determination backend gas2Gas content.By unmodified ceramic membrane, it is supported with nanometer α-Al2O3The ceramic membrane of film (is adopted
With by the method for this patent, Alumina gel concentration is 0.5g/ml), the film in the application prepared by embodiment 1～3 do completeness
Detection, its result is as shown in table 1.
The gas permeation rate and completeness of sample film prepared by table 1
As can be seen from Table 1, compared to unmodified ceramic membrane, Jing nanometer α-Al2O3The gas of the ceramic membrane after film modified
Body permeability has significantly reduction, shows that decorative layer effectively reduces the infiltration rate of ceramic membrane, that is, reduces gas and pass through
The pore size of film layer.The ZSM-5 molecular sieve nano ceramics composite membrane of the b- axles orientation that in the application prepared by embodiment 1～3
Gas permeation flux, 9 × 10-7Hereinafter, illustrate that the completeness of prepared film is higher, exist without obvious defect.
A kind of ZSM-5 molecular sieve nano ceramics composite membrane of the b- axles orientation for providing to the present invention above has carried out detailed
Introduce, specific case used herein is set forth to the principle and embodiment of the present invention, the explanation of above example
It is only intended to help and understands the method for the present invention and its core concept, it is noted that for those skilled in the art comes
Say, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and modify
Also fall in the protection domain of the claims in the present invention.
Claims (5)
1. a kind of ZSM-5 molecular sieve nano ceramics of b- axles orientation is combined membrane preparation method, it is characterised in that including following step
Suddenly：
(1) preparation of ZSM-5 molecular sieve crystal seed：With silicon source, silicon source, organic formwork agent and water as raw material, the raw material of reaction system
Mole composition is calculated as with oxide：1Al2O3:aSiO2:bTemplate:cH2O, a=10～1000, b=0.5～3, c=4.5
～100, Template are organic formwork agent, according to above-mentioned consumption, silicon source are added to the water, and stirring to being completely dissolved becomes silicon
Colloidal sol, under stirring, silicon source and organic formwork agent is progressively added drop-wise in Ludox successively, and is continued stirring until uniformly,
The pH of reactant liquor is adjusted to into 11～12, that is, ZSM-5 molecular sieve Synthesis liquid is obtained；
The ZSM-5 molecular sieve Synthesis liquid is put in reaction vessel, then reaction vessel is put into and has been warming up to 140 DEG C
Heat in～200 DEG C of heater, and react 12～100h under agitation, after completion of the reaction, reaction vessel drops naturally
Warm to room temperature, then take out ZSM-5 molecular sieve sample, clean and be dried, obtain ZSM-5 molecular sieve crystal seed；
(2) preparation of Alumina gel：Organic silicon source or inorganic silicon source are dissolved in distilled water and make Alumina gel, in Alumina gel aluminium from
Protonatomic mass concentration is 0.01～0.5g/ml；The Alumina gel solution temperature is risen to into 80 DEG C～95 DEG C, under stirring, plus
Enter shitosan dissolving so that the chitosan mass concentration in solution is 0.005～0.1g/ml, and the mixed solution is cooled to
Room temperature；
(3) preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axles orientation：Step (1) is obtained into the ZSM-5 molecular sieve
Crystal seed is added in step (2) mixed solution, the ZSM-5 molecular sieve crystal seed with the mixed solution silicon source mole
Than for 0.01～1；Mixed solution containing ZSM-5 molecular sieve crystal seed and Alumina gel is coated on into load using spin-coating method or drop-coating
External surface, is then put into carrier in heater, with 0.01～1m3The constant flow rate of/h is passed through air or oxygen, with 10
DEG C/min heating rates rise to 480 DEG C～800 DEG C, and 5～10h of constant temperature, prepare the ZSM-5 molecular sieve nanometer pottery of b- axles orientation
Porcelain composite membrane.
2. the ZSM-5 molecular sieve nano ceramics of b- axles orientation according to claim 1 is combined membrane preparation method, and its feature exists
In, the silicon source described in step (1) selected from sodium aluminate, boehmite, aluminium chloride, alumino-silicate or containing 2～4 carbon atoms
One kind in aluminium alcoholates, described organic formwork agent are selected from the one kind in TPAOH, 4-propyl bromide or triethylamine,
The one kind of described silicon source in tetraethyl orthosilicate, Ludox, silicic acid or waterglass.
3. the ZSM-5 molecular sieve nano ceramics of b- axles orientation according to claim 1 and 2 is combined membrane preparation method, and which is special
Levy and be, the organic silicon source described in step (2) is aluminium isopropoxide, described inorganic silicon source is selected from aluminium chloride, boehmite, silicon
One kind in aluminate or aluminum sulfate.
4. the ZSM-5 molecular sieve nano ceramics of b- axles orientation according to claim 1 and 2 is combined membrane preparation method, and which is special
Levy and be, the carrier described in step (3) is the ceramics of porous stainless steel or sheet.
5. the ZSM-5 molecular sieve nano ceramics of b- axles orientation according to claim 1 and 2 is combined membrane preparation method, and which is special
Levy and be, the mixed solution containing ZSM-5 molecular sieve crystal seed and Alumina gel described in step (3) adopts spin-coating method or drop-coating
Vector outside is coated on, coating thickness is 5～10 μm.
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