CN106512752B - A kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation - Google Patents
A kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation Download PDFInfo
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- CN106512752B CN106512752B CN201611100750.1A CN201611100750A CN106512752B CN 106512752 B CN106512752 B CN 106512752B CN 201611100750 A CN201611100750 A CN 201611100750A CN 106512752 B CN106512752 B CN 106512752B
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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 67
- 239000000919 ceramic Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 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
- 229920001661 Chitosan Polymers 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000009415 formwork Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000010792 warming Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 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
- 239000000243 solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- 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
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 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
- 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
- 239000000203 mixture Substances 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
- 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
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 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
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 36
- 239000007789 gas Substances 0.000 description 19
- 230000007547 defect Effects 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 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
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance 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
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 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
- 230000009286 beneficial effect Effects 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
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 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
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement 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
- 239000000700 radioactive tracer Substances 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
- 238000007873 sieving Methods 0.000 description 1
- 239000002356 single layer Substances 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
Landscapes
- 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 present invention relates to a kind of compound membrane preparation methods of ZSM-5 molecular sieve nano ceramics of b- axis orientation, comprising the following steps: (1) using silicon source, silicon source, organic formwork agent and water as raw material, ZSM-5 molecular sieve Synthesis liquid is made；Synthesis liquid obtains ZSM-5 molecular sieve crystal seed by reaction；(2) silicon source is dissolved in distilled water and Aluminum sol is made, be warming up to 80 DEG C~95 DEG C, chitosan dissolution is added；(3) ZSM-5 molecular sieve crystal seed is added in mixed solution, mixed solution is coated on carrier outer surface, carrier is put into heating device, be warming up to 480 DEG C~800 DEG C constant temperature, obtain the ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation.The advantages of preparation process condition of the present invention is mild, easy to operate, the Novel composite membrane developed, and combines orientation ZSM-5 molecular sieve film and nano ceramics film is conducive to the technological industrializations such as gas separation, purification and the separation of alcohol water low-power membrane.
Description
Technical field
The invention belongs to inorganic porous material, UF membrane and membrane catalytic technology fields, and in particular to a kind of b- axis orientation
The compound membrane preparation method of ZSM-5 molecular sieve nano ceramics.
Background technique
ZSM-5 is the wider zeolite molecular sieve of a kind of application range, it has two-dimensional channel structure, and effective aperture is about
0.55nm is suitable for a variety of 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), hydrothermal stability and chemical stability are 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 fermentation liquid, there is very high industrial application value in terms of fuel ethanol production.Contain
Transition metal hetero-atom type ZSM 5 molecular sieve film, the transition metal in duct can play good shape selective catalysis performance, table
Reveal special redox active, many redox reactions can be catalyzed.Since hetero atom type ZSM 5 molecular sieve film has
Separation and catalysis dual function, it can not only be limited to improve by balance by a certain component selectively removed in product
The reaction conversion ratio and selectivity of system also allow to carry out two reactions simultaneously in same reactor, make the production of first reaction
Object selectively penetrates film and participates in second reaction, realizes catalysis and isolated combination, thus in membrane reactor and micro-
Type reactor has huge application prospect in field.
In recent years, type ZSM 5 molecular sieve film UF membrane, Membrane catalysis, chemical sensor and in terms of
Using increasingly wider.The experimental results show the micro-structure of zeolite molecular sieve film and crystal orientation directly affect its separate with
Catalytic performance.Since the type ZSM 5 molecular sieve intracrystalline pore road structure of different orientation differs greatly, type ZSM 5 molecular sieve film
Orientation can seriously affect its mass transfer and characteristic electron, and then it is separated and catalytic performance generate tremendous influence.So closely
The preparation of ZSM-5 type orientation molecular sieve membrane is increasingly by the concern of people over year.Although in the nearly more than ten years, the system of molecular screen membrane
Standby technique is rapidly developed, but due to the limitation of carrier flatness etc., type ZSM 5 molecular sieve film preparation and
There is also many insoluble problems for application aspect.
Summary of the invention
The purpose of the present invention is to provide a kind of b- axis orientation the compound membrane preparation method of ZSM-5 molecular sieve nano ceramics,
The preparation method overcomes the technical bottleneck in existing ZSM-5 molecular sieve film preparation technique, and process conditions are mild, process it is simple and
Novel composite membrane low in cost, preparing combines the advantages of orientation ZSM-5 molecular sieve film is with 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 achieve the above-mentioned object of the invention, technical scheme is as follows:
The object of the present invention is to provide a kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation, packets
Include following steps:
(1) preparation of ZSM-5 molecular sieve crystal seed: using 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, and according to above-mentioned dosage, silicon source is added to the water, and stirring is to being completely dissolved into
Silicon source and organic formwork agent are successively gradually added drop-wise in silica solution under stirring for silica solution, and continued stirring until
It is even, the pH of reaction solution is adjusted to 11~12, ZSM-5 molecular sieve Synthesis liquid is obtained；
The ZSM-5 molecular sieve Synthesis liquid is put into reaction vessel, then reaction vessel is put into and has been warming up to
It is heated in 140 DEG C~200 DEG C of heating device, and reacts 12~100h under agitation, after completion of the reaction, reaction vessel is certainly
It so is cooled to room temperature, ZSM-5 molecular sieve sample, cleaning and drying is then taken out, obtains ZSM-5 molecular sieve crystal seed；
(2) preparation of Aluminum sol: organic silicon source or inorganic silicon source are dissolved in distilled water and Aluminum sol are made, in Aluminum sol
Aluminium ion mass concentration is 0.01~0.5g/ml；The Aluminum sol solution temperature is risen to 80 DEG C~95 DEG C, in stirring
Under, chitosan dissolution is added, so that the chitosan mass concentration in solution is 0.005~0.1g/ml, and the mixed solution is cold
But to room temperature；
(3) the ZSM-5 molecular sieve crystal seed is made in step (1) to be added in step (2) described mixed solution, it is described
The molar ratio of silicon source is 0.01~1 in ZSM-5 molecular sieve crystal seed and the mixed solution；Will containing ZSM-5 molecular sieve crystal seed and
The mixed solution of Aluminum sol is coated on carrier outer surface using spin-coating method or drop-coating, and then carrier is put into heating device,
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 rate, and permanent
5~10h of temperature prepares the ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation.
In the application, signified room temperature is 20 DEG C~28 DEG C.The effect of chitosan is to make nano ceramics film and ZSM-5 molecule
Sieving crystal can preferably combine in carrier surface.
It is compound that the application can prepare fine and close ZSM-5 molecular sieve nano ceramics on macropore ceramics or stainless steel carrier
Film, and the composition by adjusting Synthesis liquid, hydrothermal synthesis temperature and the synthesis such as the applying structure guiding agent-chitosan item on carrier
Part promotes molecular sieve crystal oriented growth, while can reach the purpose for adjusting film thickness, finally directly prepares on macropore carrier
The completeness of ZSM-5 molecular sieve film can be improved in complete orientation ZSM-5 molecular sieve nano ceramics composite membrane out, and can be effective
Reduce production cost.
Preferably, silicon source described in step (1) is selected from sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or contains 2
One of the aluminium alcoholates of~4 carbon atoms, the organic formwork agent are selected from tetrapropylammonium hydroxide, 4-propyl bromide or three
One of ethamine, the silicon source are selected from one of ethyl orthosilicate, silica solution, silicic acid or waterglass.
Preferably, organic silicon source described in step (2) is aluminium isopropoxide, and the inorganic silicon source is aluminium chloride or sulfuric acid
Aluminium.
Preferably, the carrier is the ceramics of porous stainless steel or sheet.
Preferably, the mixed solution containing ZSM-5 molecular sieve crystal seed and Aluminum sol described in step (3) using spin-coating method or
Drop-coating is coated on vector outside, and coating thickness is 5~10 μm.
The beneficial effects of the present invention are:
(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；
It (2) is the ZSM-5 molecular sieve film of specific b axis orientation prepared by, process conditions of the invention are mild, operate 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 advantages of rice ceramic membrane, while being more advantageous to the technological industrializations such as gas separation, purification and the separation of alcohol water low-power membrane.
Detailed description of the invention
Fig. 1 is ceramic monolith employed in the present invention and the nanometer α-Al for being covered with different-thickness2O3The SEM of film shines
Piece: (a) being unmodified ceramic monolith plane SEM photograph；(b) the nanometer α-for using concentration to prepare for 0.01g/ml Aluminum sol
Al2O3Thin film planar SEM photograph；(c) the nanometer α-Al for using concentration to prepare for 0.5g/ml Aluminum sol2O3Thin film planar SEM shines
Piece；(d) the nanometer α-Al for using concentration to prepare for 0.01g/ml Aluminum sol2O3Thin-membrane section SEM photograph；(e) use concentration for
Nanometer α-the Al of 0.5g/ml Aluminum sol preparation2O3Thin-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；
Fig. 7 is the equipment schematic diagram of single-component gas permeability test.
Specific embodiment
Below with reference to specific example, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit the scope of protection of the present invention.The improvement and tune that technical staff makes according to the present invention in practical applications
It is whole, still fall within protection scope of the present invention.
Except special instruction, the equipment and reagent that the present invention uses are the art regular market purchase product.
A kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation, includes the following steps:
(1) preparation of ZSM-5 molecular sieve crystal seed: using 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, and according to above-mentioned dosage, silicon source is added to the water, and stirring is to being completely dissolved into
Silicon source and organic formwork agent are successively gradually added drop-wise in silica solution under stirring for silica solution, and continued stirring until
It is even, the pH of reaction solution is adjusted to 11~12, ZSM-5 molecular sieve Synthesis liquid is obtained；
The ZSM-5 molecular sieve Synthesis liquid is put into reaction vessel, then reaction vessel is put into and has been warming up to
It is heated in 140 DEG C~200 DEG C of heating device, and reacts 12~100h under agitation, after completion of the reaction, reaction vessel is certainly
It so is cooled to room temperature, ZSM-5 molecular sieve sample, cleaning and drying is then taken out, obtains ZSM-5 molecular sieve crystal seed；
(2) preparation of Aluminum sol: organic silicon source or inorganic silicon source are dissolved in distilled water and Aluminum sol are made, in Aluminum sol
Aluminium ion mass concentration is 0.01~0.5g/ml；The Aluminum sol solution temperature is risen to 80 DEG C~95 DEG C, in stirring
Under, chitosan dissolution is added, so that the chitosan mass concentration in solution is 0.005~0.1g/ml, and the mixed solution is cold
But to room temperature；
(3) the ZSM-5 molecular sieve crystal seed is made in step (1) to be added in step (2) described mixed solution, it is described
The molar ratio of silicon source is 0.01~1 in ZSM-5 molecular sieve crystal seed and the mixed solution；Will containing ZSM-5 molecular sieve crystal seed and
The mixed solution of Aluminum sol is coated on carrier outer surface using spin-coating method or drop-coating, and then carrier is put into heating device,
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 rate, and permanent
5~10h of temperature prepares the ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation.
One in aluminium alcoholates of the silicon source selected from sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or 2~4 carbon atoms
Kind, preferred aluminium isopropoxide and boehmite.Organic formwork agent is selected from tetrapropylammonium hydroxide (TPAOH), tetrapropyl bromination
One of ammonium (TPABr) or triethylamine (TEA).Silicon source in ethyl orthosilicate, silica solution, silicic acid or waterglass one
Kind.
It is to further explanation of the invention, but content not thereby limiting the invention below.
Embodiment illustrates the compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation of the 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 be respectively adopted is AlCl3And ethyl orthosilicate, while using triethylamine for template.It is added in pure water a certain amount of
NaOH makes its complete hydrolysis so that the pH value of solution dissolves ethyl orthosilicate 5h under 11~12, stirring condition；To aqueous solution
The AlCl of proportional quantity is added after clarification3, stirring and dissolving 3h, after the dissolution completely of each substance, adjust the pH value of reaction solution 11~
12, and aging 10h at room temperature, then it is added in reaction kettle.Reaction kettle is placed in the baking oven for being warming up to 140 DEG C, and
100h is reacted in stirring condition, after completion of the reaction, reaction kettle is naturally cooling to room temperature, ZSM-5 molecular sieve sample is then taken out, and
Wash with distilled water, it is dried to obtain ZSM-5 molecular sieve crystal seed.
(2) preparation of Aluminum sol
Under agitation, aluminium isopropoxide is made an addition in distilled water, makes aluminium ion mass concentration 0.5g/ in solution
Ml, and the nitric acid that 0.5g concentration is 98% is added dropwise, so that solution ph is 2, and continues to stir 2h, then it is added in reaction kettle simultaneously
Reaction kettle is placed in the baking oven for being warming up to 150 DEG C；
Prepared Aluminum sol solution is warming up to 95 DEG C, then under agitation, chitosan dissolution is added, so that molten
Chitosan concentration in liquid is that mixed solution is cooled to room temperature by 0.1g/ml when chitosan is completely dissolved in uniform state.
(3) preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation
Under agitation, ZSM-5 molecular sieve crystal seed is made in step (1) and is added to mixing prepared in step (2)
In solution, the additive amount of ZSM-5 molecular sieve crystal seed and mixed solution presses molar ratio of material ZSM-5:Al2O3=1:1, and persistently stir
5h is mixed, uniform mixed liquor is become；
Using drop-coating, prepared uniform mixed liquor is coated on ceramic monolith outer surface, coating thickness is 5 μm, and
The carrier after coating is put into temperature programmed control atmosphere furnace afterwards, with 0.01m3The constant flow rate of/h is passed through air or oxygen, with 10
DEG C/min heating rate rises to 800 DEG C, and constant temperature 10h, keeps Aluminum sol fully oxidized, prepare the single layer ZSM-5 of b- axis orientation
Molecular sieve nano ceramics composite membrane.
SEM detection, result such as Fig. 2 institute are carried out to ZSM-5 molecular sieve nano ceramics composite membrane prepared by embodiment 1
Show, prepared ZSM-5 molecular sieve film layer flatness is higher, no significant defect, and molecular sieve partial size is 0.5 μm.
Embodiment 2
(1) preparation of ZSM-5 molecular sieve crystal seed
It is substantially the same manner as Example 1, it is different be to prepare ZSM-5 molecular sieve Synthesis liquid during, used aluminium
Source and silicon source are respectively boehmite and waterglass, and use 4-propyl bromide for template.
(2) preparation of Aluminum sol
Essentially identical with implementing 1, different is using aluminum sulfate as silicon source.
(3) preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation
Substantially the same manner as Example 1, different is that used carrier is porous stainless steel, and air velocity becomes 1m3/
H, calcination temperature become 480 DEG C.
SEM detection, result such as Fig. 3 institute are carried out to ZSM-5 molecular sieve nano ceramics composite membrane prepared by embodiment 2
Show, prepared ZSM-5 molecular sieve film layer flatness is higher, no significant defect, and molecular sieve partial size is 0.4 μm.
Embodiment 3
(1) preparation of ZSM-5 molecular sieve crystal seed
It is substantially the same manner as Example 1, it is different be to prepare ZSM-5 molecular sieve Synthesis liquid during, used aluminium
Source and silicon source difference sodium aluminate and silica solution, template is using tetrapropylammonium hydroxide.Meanwhile the material formula of Synthesis liquid
For 1Al2O3:10SiO2:0.5TPAOH:4.5H2O, reaction temperature are set as 200 DEG C, reaction time 12h.
(2) preparation of Aluminum sol
It is substantially the same manner as Example 1, it is different to be using aluminium chloride as silicon source, and with and adjust silicon source additive amount,
Make aluminium ion mass concentration 0.01g/ml in solution, Aluminum sol is warming up to 80 DEG C；Chitosan additive amount is had adjusted, so that solution
In chitosan concentration be 0.005g/ml.
(3) preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation
The additive amount for being to have adjusted ZSM-5 molecular sieve substantially the same manner as Example 1, different, so that molar ratio of material
ZSM-5:Al2O3For 0.01:1；Mixed solution is coated on carrier surface by spin-coating method, and coating thickness is 10 μm, and using heating speed
Muffle furnace is warming up to 800 DEG C for 10 DEG C/min by rate, and calcines 5h at this temperature.
SEM detection, result such as Fig. 4 institute are carried out to ZSM-5 molecular sieve nano ceramics composite membrane prepared by embodiment 3
Show, prepared ZSM-5 molecular sieve film layer flatness is higher, no significant defect, and molecular sieve partial size is 2.5 μm.
Embodiment 4
ZSM-5 molecular sieve nano ceramics composite membrane, ZSM-5 molecular sieve Synthesis liquid proportion are prepared using Vacuum-assisted method method
And it is same as Example 1 with synthesis liquid preparing process.It is different be used in silicon source be aluminium isopropoxide, and be by without
The ceramic monolith of modification, which is directly placed into Synthesis liquid, reacts 100h, prepares ZSM-5 molecular sieve nano ceramics composite membrane.Its result
As shown in figure 5, there is biggish defect thereon since carrier surface is unmodified, prepared ZSM-5 molecular sieve film is caused to have
Local location collapses, and defect is obvious.
Embodiment 5
(1) preparation of ZSM-5 molecular sieve
ZSM-5 molecular sieve Synthesis liquid with when with synthesis liquid preparing process it is same as Example 1, 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 unmodified ceramic monolith surface；The ceramic monolith for being supported with molecular sieve seed is then put into ZSM-5 points
In son sieve Synthesis liquid, synthesizes formula of liquid and preparation process is same as Example 1.
Its result leads to prepared ZSM-5 molecular sieve film table as shown in fig. 6, since carrier surface defect is more obvious
Face is rough and uneven in surface, and there are ceramic matrix exposing in some areas, and defect is more obvious.
Fig. 1 is ceramic monolith employed in the present invention and the nanometer α-Al for being covered with different-thickness2O3The SEM of film shines
Piece: (a) being unmodified ceramic monolith plane SEM photograph；(b) the nanometer α-for using concentration to prepare for 0.01g/ml Aluminum sol
Al2O3Thin film planar SEM photograph；(c) the nanometer α-Al for using concentration to prepare for 0.5g/ml Aluminum sol2O3Thin film planar SEM shines
Piece；(d) the nanometer α-Al for using concentration to prepare for 0.01g/ml Aluminum sol2O3Thin-membrane section SEM photograph；(e) use concentration for
Nanometer α-the Al of 0.5g/ml Aluminum sol preparation2O3Thin-membrane section SEM photograph.
By scheming (a) as it can be seen that without the ceramic monolith surface relief injustice that Aluminum sol is modified, and between carrier surface particulate matter
Cohesive force is weaker.By scheming (b)~(e) as it can be seen that as coating nanometer α-Al2O3After film, the flatness of carrier surface, which has, significantly to be changed
It is kind, and the flatness on surface enhances with the increase of Aluminum sol concentration.Meanwhile nanometer α-Al2O3The thickness of film is also with Aluminum sol
The increase of concentration and increase (when Aluminum sol concentration is improved by 0.01g/ml to 0.5g/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- axis orientation
The application uses one-component gas permeating method (Applied Surface Science, 2008,254:2353-
2358) completeness of the synthesized composite molecular sieve film of (testing leakage method) detection, 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.It tests in the experiment of leakage method, in feed end N2Gas is as tracer gas, in infiltration end H2Gas is permeated as purge gass by measurement
The N at end2Gas content can determine that the completeness of molecular screen membrane.It tests in the experiment of leakage method, membrane cisterna temperature is 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 is directly entered gas-chromatography,
N in on-line determination backend gas2Gas content.By unmodified ceramic membrane, it is supported with a nanometer α-Al2O3The ceramic membrane of film (is adopted
With the method by this patent, Aluminum sol concentration does completeness for film prepared by Examples 1 to 3 in 0.5g/ml), the application
Detection, the results are 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, through nanometer α-Al2O3The gas of ceramic membrane after film modified
Body permeability has apparent 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 for the b- axis orientation that in the application prepared by Examples 1 to 3
Gas permeation flux, 9 × 10-7Hereinafter, the completeness of film prepared by explanation is higher, no apparent defect exists.
A kind of ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation provided by the invention is carried out above detailed
It introduces, used herein a specific example illustrates the principle and implementation of the invention, the explanation of above embodiments
It is merely used to help understand method and its core concept of the invention, it is noted that those skilled in the art are come
It says, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
It also falls within the protection scope of the claims of the present invention.
Claims (5)
1. a kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation, which is characterized in that including following step
It is rapid:
(1) preparation of ZSM-5 molecular sieve crystal seed: using 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, and according to above-mentioned dosage, silicon source is added to the water, and stirring is to being completely dissolved as silicon
Silicon source and organic formwork agent are successively gradually added drop-wise in silica solution by colloidal sol under stirring, and are continued stirring until uniformly,
The pH of reaction solution is adjusted to 11~12, ZSM-5 molecular sieve Synthesis liquid is obtained；
The ZSM-5 molecular sieve Synthesis liquid is put into reaction vessel, then reaction vessel is put into and has been warming up to 140 DEG C
It is heated in~200 DEG C of heating device, and reacts 12~100h under agitation, after completion of the reaction, reaction vessel drops naturally
It warms to room temperature, then takes out ZSM-5 molecular sieve sample, cleaning and drying, obtain ZSM-5 molecular sieve crystal seed；
(2) preparation of Aluminum sol: being dissolved in organic silicon source or inorganic silicon source in distilled water and Aluminum sol be made, in Aluminum sol aluminium from
Protonatomic mass concentration is 0.01~0.5g/ml；The Aluminum sol solution temperature is risen to 80 DEG C~95 DEG C, under stirring, is added
Enter chitosan dissolution, so that the chitosan mass concentration in solution is 0.005~0.1g/ml, and the mixed solution is cooled to
Room temperature；
(3) ZSM-5 molecular sieve preparation of the ZSM-5 molecular sieve nano ceramics composite membrane of b- axis orientation: is made in step (1)
Crystal seed is added in step (2) described mixed solution, mole of silicon source in the ZSM-5 molecular sieve crystal seed and the mixed solution
Than being 0.01~1；Mixed solution containing ZSM-5 molecular sieve crystal seed and Aluminum sol is coated on load using spin-coating method or drop-coating
Carrier is then put into heating device by external surface, with 0.01~1m3The constant flow rate of/h is passed through air or oxygen, with 10
DEG C/min heating rate rises to 480 DEG C~800 DEG C, and 5~10h of constant temperature, prepare the ZSM-5 molecular sieve nanometer pottery of b- axis orientation
Porcelain composite membrane.
2. the compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation according to claim 1, feature exist
Sodium aluminate, boehmite, aluminium chloride, alumino-silicate or containing 2~4 carbon atoms are selected from, silicon source described in step (1)
One of aluminium alcoholates, the organic formwork agent are selected from one of tetrapropylammonium hydroxide, 4-propyl bromide or triethylamine,
The silicon source is selected from one of ethyl orthosilicate, silica solution, silicic acid or waterglass.
3. the compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation according to claim 1 or 2, special
Sign is that organic silicon source described in step (2) is aluminium isopropoxide, and the inorganic silicon source is selected from aluminium chloride, boehmite, silicon
One of aluminate or aluminum sulfate.
4. the compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation according to claim 1 or 2, special
Sign is that carrier described in step (3) is the ceramics of porous stainless steel or sheet.
5. the compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation according to claim 1 or 2, special
Sign is that the mixed solution containing ZSM-5 molecular sieve crystal seed and Aluminum sol described in step (3) uses spin-coating method or drop-coating
It is coated on vector outside, coating thickness is 5~10 μm.
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| US6494326B1 (en) * | 2000-06-15 | 2002-12-17 | Sandia Corporation | Composite zeolite membranes |
| CN101099924A (en) * | 2006-07-06 | 2008-01-09 | 中国科学院大连化学物理研究所 | Method for preparing chitosan/ZSM-5 molecular compound film |
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