CN103058213A - Preparation method of LTA type molecular sieve film and prepared LTA type molecular sieve film - Google Patents
Preparation method of LTA type molecular sieve film and prepared LTA type molecular sieve film Download PDFInfo
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Abstract
The invention relates to a preparation method of an LTA type molecular sieve film and the prepared LTA type molecular sieve film. According to the method, through a covalent bonding reaction of a substrate having a hydroxyl on the surface and organosilane having halogenated alkyl and active groups capable of covalently bonding with the hydroxyl, the surface of the substrate is introduced with a silane coupling body having the halogenated alkyl, thereby obtaining the substrate with a functionally modified surface. The method further comprises contacting the substrate having the functionally modified surface with a preparation liquid containing silica-alumina precursors used for synthesizing the LTA type molecular sieve film, so that the halogenated alkyl of the silane coupling body on the surface of the substrate is subjected to a covalent bonding reaction with the silica-alumina precursors in a hydrothermal synthesis, thereby preparing the LTA type molecular sieve film on the surface of the substrate. The method and the prepared LTA type molecular sieve film are suitable for separation of mixed gases containing more than two kinds of gases selected from H2, N2, CO2 and low-carbon alkane gas.
Description
Technical field
The invention belongs to the molecular screen membrane field that is applied to gas delivery, liquid separation, be specifically related to a kind of preparation method of LTA type molecular screen membrane, reach the LTA type molecular screen membrane that described method makes.
Background technology
Molecular sieve refer to a series of take silica, aluminum-oxygen tetrahedron as basic structural unit, have the general designation of the inorganic microporous crystalline material of regular pore passage structure.Molecular sieve has been widely used as sorbent material, ion-exchanger and catalyzer in industry.In addition, the excellent properties of molecular sieve is so that it becomes good mineral membrane parting material recently.Molecular sieve has many advantages as inorganic material film.Molecular sieve has the neat duct of standard, and pore size distribution is single, and the molecular dimension size of the pore size of molecular sieve size and many important industrial raw material is close, and the gas/liquid molecule can spread by molecule screening or the type of selecting and be separated.Molecular sieve has good chemical stability and thermostability.The diversity of molecular sieve structure causes the diversity of its character, such as the different pore size size, and different hydrophilic and hydrophobics, thereby can select suitable molecular screen membrane according to different separation requirement.
The modifiability of molecular sieve pore passage and hole outside surface causes the adjustable sex change of molecular sieve bore diameter and absorption property.Molecular sieve has good catalytic activity, thereby molecular screen membrane can realization response-isolation integral.So molecular screen membrane has a wide range of applications, all can be applied in gas delivery, vapor removal, liquid separation, membrane catalytic reaction, Subjective and Objective reaction, environment protection, Life Engineering, electrode and sensor various fields.Just because of molecular screen membrane has unique characteristic and application prospect widely, the research of molecular screen membrane causes people's extensive concern and interest, since the people such as Suzuki reported since synthesizing molecular sieve film on the porous support with the patent form first in 1987, till now, people successfully synthesize MFI, FER, MOR, LTA type, FAU type, CHA type, T-shaped, L-type, P type, the 20 different kinds of molecules sieve membranes such as TS-1, UTD-1 in variety carrier.
In the 20 different kinds of molecules sieve membranes of having reported, wherein synthetic the and applied research of octatomic ring LTA type (Linde Type A) molecular screen membrane has caused people's very big interest.The aperture of LTA molecular screen membrane is about 0.4nm, and pore size approaches or less than the kinetic diameter of low-carbon alkanes quasi-molecule, so H
2, N
2Can be separated by selecting shape diffusion or molecule with separating of lower alkanes hydro carbons.In addition, LTA type molecular screen membrane has lower silica alumina ratio, and very strong wetting ability is arranged, and water can well be separated with non-polar molecule with organism or polar molecule.So the synthetic and applied research of LTA type molecular screen membrane has caused people's very big interest.
Synthetic Vacuum-assisted method and the diauxic growth of mainly comprising of LTA molecular screen membrane synthesizes.The Vacuum-assisted method method is also referred to as direct method, refers to directly matrix be put into reaction soln the method for Hydrothermal Synthesis molecular screen membrane under certain temperature and pressure.The Vacuum-assisted method method is present the most frequently used synthetic method, but because Vacuum-assisted method is very responsive to chemistry, the physicals of synthesis condition and matrix, the minor alteration of a certain synthesis condition all can affect the performance of molecular screen membrane, so usually be difficult to the molecular screen membrane of synthesized high-performance.The diauxic growth synthesis method is also referred to as crystal seed method, refers to introduce the homodisperse molecular sieve crystal seed of one deck at matrix surface in advance, and then the method for Hydrothermal Synthesis molecular screen membrane.The diauxic growth synthesis method is introduced the uniform molecular sieve crystal seed of one deck so that nucleation centre to be provided at matrix surface, can separate nucleation process and crystal growing process, suppresses nucleus and is transformed into other crystal, thereby can improve the quality of synthesizing molecular sieve film.The performance of the synthetic film of diauxic growth and the quality of crystal seed layer are closely related, the bonding forces of the size of crystal seed, the thickness of crystal seed layer, crystal seed layer and carrier etc. all can produce material impact to the performance of film, particularly introduce the homodisperse molecular sieve crystal seed of one deck in membrane surface and are unfavorable for the scale operation in industrial production of LTA molecular screen membrane.
So one the LTA molecular screen membrane synthetic method of simple and effective is the basis of realizing LTA molecular screen membrane scale operation and application.The growth mechanism of molecular screen membrane shows, the growth of molecular screen membrane is a heterogeneous nucleation process, and namely the aluminate ion in the synthetic liquid and silicate ion presoma form molecular screen membrane in crystallization subsequently at first in the matrix surface nucleation.So promote molecular sieve significant to the growth that promotes molecular screen membrane in the matrix surface nucleation.
Summary of the invention
The objective of the invention is to realize the scale operation of LTA molecular screen membrane, and not introducing to finish the LTA molecular screen membrane under the homodisperse molecular sieve crystal seed of one deck synthetic, therefore first aspect present invention provides first a kind of preparation method of LTA type molecular screen membrane, it is characterized in that, described method comprises following steps:
(a) matrix that has a hydroxyl by the surface with have haloalkyl and can with the covalent bonding reaction of the organosilane of the active group of hydroxyl covalent bonding, thereby introduce the silane linker with haloalkyl at matrix surface, obtain the surface through the matrix of functional modification; And
(b) above-mentioned surface is contacted with the preparation liquid that contains for the synthesis of the sial presoma of LTA type molecular screen membrane through the matrix of functional modification, make the described haloalkyl that is arranged in the silane linker of matrix surface carry out the covalent bonding reaction at Hydrothermal Synthesis and sial presoma, thereby prepare LTA type molecular sieve rete at matrix surface, and therefore make LTA type molecular screen membrane, it comprise matrix, LTA type molecular sieve rete and be positioned at the two and with the silane linker that removes halogen of matrix and the equal covalent bonding of sieve membrane layer.
In the present invention, term " can with matrix surface hydroxyl covalent bonding active group " thus be included in after the hydrolysis and the group (such as methoxyl group, oxyethyl group etc.) of the hydroxyl condensation of matrix surface dehydration with the matrix covalent bonding, thereby and direct by with the hydroxyl condensation of matrix surface and the group of matrix covalent bonding (for example halogen radical).
In the present invention, term " haloalkyl " refers to the terminal alkyl that is replaced by halogen (F, Cl, Br or I).
In another preference, organosilane comprises one or two or more kinds in 3-r-chloropropyl trimethoxyl silane (being called for short CPTMS), 3-chloropropyl trichloro-silane (being called for short CPTCS), 3-chloropropyl dimethoxy-methyl silane (being called for short CPDMS), 3-chloropropyl dimethylchlorosilane (being called for short CPCS), 3-bromopropyl Trimethoxy silane (being called for short BPTMS), 3-bromopropyl trichlorine base silane (being called for short BPPCS), the 3-iodine propyl trimethoxy silicane (being called for short IPTMS).
In the present invention, term " removes the silane linker of halogen " and refers to aforementioned organosilane behind its active group and the matrix surface hydroxyl covalent bonding and the multivalence residue (multivalent residue) that forms behind haloalkyl and the sial presoma covalent bonding.
In another preference, preparation liquid comprises Na
2O, Al
2O
3, SiO
2And H
2O, and described sial presoma comprises NaAlO
2And Na
2SiO
3Aquo complex.
In another preference, described preparation liquid is to obtain by following steps: sodium hydroxide is dissolved in the distilled water, adds aluminium foil and stir the formation aluminum solutions; Silicon sol is added to is mixed to get silicon solution in the pre-heated distilled water; And with mixing in the described aluminum solutions adding silicon solution, comprise Na thereby make
2O, Al
2O
3, SiO
2And H
2The preparation liquid of O.
In another preference, Na
2O, Al
2O
3, SiO
2And H
2The mole ratio of O is (7.5-50): (1-2.5): (5-10): (300-1000).More preferably be (7.5-50): (1-2.5): (5-10): (500-1000).
In another preference, four mole ratio is 50:1:5:1000.
In another preference, four mole ratio is 3:1:2:200.
In another preference, matrix is one or two or more kinds in porous alumina ceramic, porous titanium dioxide ceramic, porous stainless steel disc, stainless (steel) wire, tetrafluoroethylene (PTFE) substrate, the glass substrate.
In another preference, matrix is porous alumina ceramic.
In another preference, the temperature of reaction of step (a) is 353-393K.
In another preference, the temperature of reaction of step (b) is 323-373K.
In another preference, step (b) is that the mode by conventional heating (such as air dry oven) heats, and temperature of reaction is 323-373K, and the reaction times is 2-60 hour.
In another preference, step (b) is that the mode by microwave heating (such as microwave oven) heats, and temperature of reaction is 323-353K, and the reaction times is 0.5-2 hour.
Based on aforementioned preparation method of the present invention, second aspect present invention provides a kind of LTA type molecular screen membrane, it is characterized in that described molecular sieve comprise matrix, LTA type molecular sieve rete and be positioned at the two and with the silane linker that removes halogen of matrix and the equal covalent bonding of sieve membrane layer, and obtain by aforementioned invention preparation method.
In another preference, the thickness of LTA type molecular sieve rete is between 2-5 μ m.
In another preference, LTA type molecular screen membrane is for H
2, N
2, CO
2Reach the separation of the mixed gas more than two kinds in the low-carbon alkanes gas.
In another preference, LTA type molecular screen membrane is for H
2/ CO
2, H
2/ N
2, H
2/ CH
4And H
2/ C
3H
8The separation factor of mixed gas all is higher than the gloomy spread coefficient of corresponding anger (Knudsen coefficients).
In another preference, LTA type molecular screen membrane is for H
2/ CO
2The separation factor of mixed gas is between 6.4 to 7.6.
In another preference, LTA type molecular screen membrane is for H
2/ N
2The separation factor of mixed gas is between 6.2 to 7.0.
In another preference, LTA type molecular screen membrane is for H
2/ CH
4The separation factor of mixed gas is between 4.8 to 5.5.
In another preference, LTA type molecular screen membrane is for H
2/ C
3H
8The separation factor of mixed gas is between 14.3 to 15.8.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can making up mutually between specifically described each technical characterictic in below (eg embodiment), thus consist of new or preferred technical scheme.As space is limited, this tired stating no longer one by one.
Description of drawings
Fig. 1 is that the gained photo is identified by SEM in the surface of the LTA type molecular screen membrane that makes of the explanation embodiment of the invention 1.
Fig. 2 is that the section of the LTA type molecular screen membrane that makes of the explanation embodiment of the invention 1 is identified the gained photo by SEM.
Fig. 3 is the LTA type molecular screen membrane that supports of porous alumina ceramic that explanation (a) LTA zeolites product, (b) embodiment 1 make and (c) X-ray diffraction spectrum of porous alumina ceramic matrix.
Fig. 4 is the gas separating property test result of the LTA type molecular screen membrane that makes of explanation embodiment 1.
Embodiment
The inventor finds through extensive and deep research, by introducing first organosilane with haloalkyl in matrix surface and obtaining the modified matrix in surface (introducing the silane linker with haloalkyl in matrix surface), the haloalkyl by silane linker on the matrix prepares with LTA type molecular screen membrane in Hydrothermal Synthesis that the sial presoma (comprises NaAlO in the liquid more afterwards
2And Na
2SiO
3Aquo complex) hydroxyl between covalent bonding, thereby can obtain even compact and the good molecular screen membrane of separation performance, this method can improve the synthetic repeatability of LTA molecular screen membrane, realizes scale operation and the application of LTA molecular screen membrane.Finished on this basis the present invention.
The preparation method of LTA type molecular screen membrane
The preparation method of LTA type molecular screen membrane of the present invention comprises following steps:
(a) matrix that has a hydroxyl by the surface with have haloalkyl and can with the covalent bonding reaction of the organosilane of the active group of hydroxyl covalent bonding, thereby introduce the silane linker with haloalkyl at matrix surface, obtain the surface through the matrix of functional modification; And
(b) above-mentioned surface is contacted with the preparation liquid that contains for the synthesis of the sial presoma of LTA type molecular screen membrane through the matrix of functional modification, make the described haloalkyl that is arranged in the silane linker of matrix surface carry out the covalent bonding reaction at Hydrothermal Synthesis and sial presoma, thereby prepare LTA type molecular sieve rete at matrix surface, and therefore make LTA type molecular screen membrane, it comprise matrix, LTA type molecular sieve rete and be positioned at the two and with the silane linker that removes halogen of matrix and the equal covalent bonding of sieve membrane layer.
In another preference, organosilane comprises one or two or more kinds in 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl trichloro-silane, 3-chloropropyl dimethoxy-methyl silane, 3-chloropropyl dimethylchlorosilane, 3-bromopropyl Trimethoxy silane, 3-bromopropyl trichlorine base silane, the 3-iodine propyl trimethoxy silicane.
In another preference, preparation liquid comprises Na
2O, Al
2O
3, SiO
2And H
2O, and described sial presoma comprises NaAlO
2And Na
2SiO
3Aquo complex.
In another preference, preparation liquid is to obtain by following steps: sodium hydroxide is dissolved in the distilled water, adds aluminium foil and stir the formation aluminum solutions; Silicon sol is added to is mixed to get silicon solution in the pre-heated distilled water; And with mixing in the described aluminum solutions adding silicon solution, comprise Na thereby make
2O, Al
2O
3, SiO
2And H
2The preparation liquid of O.
In another preference, Na
2O, Al
2O
3, SiO
2And H
2The mole ratio of O is (7.5-50): (1-2.5): (5-10): (500-1000).More preferably be (7.5-50): (1-2.5): (5-10): (500-1000).
In another preference, four mole ratio is 50:1:5:1000.
In another preference, four mole ratio is 3:1:2:200.
In another preference, matrix is one or two or more kinds in porous alumina ceramic, porous titanium dioxide ceramic, porous stainless steel disc, stainless (steel) wire, tetrafluoroethylene (PTFE) substrate, the glass substrate.
In another preference, matrix is porous alumina ceramic.
In another preference, the temperature of reaction of step (a) is 353-393K.
In another preference, the temperature of reaction of step (b) is 323-373K.
In another preference, step (b) is that the mode by conventional heating (such as air dry oven) heats, and temperature of reaction is 323-373K, and the reaction times is 2-60 hour.
In another preference, step (b) is that the mode by microwave heating (such as microwave oven) heats, and temperature of reaction is 323-353K, and the reaction times is 0.5-2 hour.
LTA type molecular screen membrane
Based on aforementioned preparation method of the present invention, the LTA type molecular screen membrane that the present invention prepares also is novel, its comprise matrix, LTA type molecular sieve rete and be positioned at the two and with the silane linker that removes halogen of matrix and the equal covalent bonding of sieve membrane layer, and obtain by aforementioned invention preparation method.
In another preference, the thickness of LTA type molecular sieve rete is between 2-5 μ m.
In another preference, molecular screen membrane is for H
2, N
2, CO
2Reach the separation of the mixed gas more than two kinds in the low-carbon alkanes gas.
In another preference, molecular sieve is for H
2/ CO
2, H
2/ N
2, H
2/ CH
4And H
2/ C
3H
8The separation factor of mixed gas all is higher than the gloomy spread coefficient of corresponding anger (Knudsen coefficients).
In another preference, LTA type molecular screen membrane is for H
2/ CO
2The separation factor of mixed gas is between 6.4 to 7.6.
In another preference, LTA type molecular screen membrane is for H
2/ N
2The separation factor of mixed gas is between 6.2 to 7.0.
In another preference, LTA type molecular screen membrane is for H
2/ CH
4The separation factor of mixed gas is between 4.8 to 5.5.
In another preference, LTA type molecular screen membrane is for H
2/ C
3H
8The separation factor of mixed gas is between 14.3 to 15.8.
Main beneficial effect of the present invention comprises:
(1) the inventive method is not introduced the uniform crystal seed layer of one deck at matrix with not costing power and accurate control, but the organosilane that passes through the double functional group connects the sial presoma of matrix and synthetic LTA molecular screen membrane under Hydrothermal Synthesis, thereby so that directly nucleation and growth on matrix of the sial presoma of LTA molecular sieve, therefore operate simple and easyly, be suitable for industry and amplify.
(2) the LTA type molecular screen membrane that makes of the inventive method is even compact, does not have stray crystal to generate, and the LTA type molecular screen membrane that this method makes is particularly suitable for H
2, N
2, CO
2And the separation of the mixed gas of low-carbon alkanes gas etc., its separation factor for these mixed gas all is higher than the gloomy spread coefficient of corresponding anger, has good separation selectivity.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.
＜material source 〉
1. porous alumina and titanium dioxide ceramic: available from German Hermsdorf company, diameter is 18mm, thickness 1.0mm; Porous Stainless Steel: available from U.S. Mott company, diameter is 18mm, thickness 1.0mm; Tetrafluoroethylene (PTFE) substrate and glass substrate, self-control, diameter is 18mm, thickness 1.0mm.
2.3-r-chloropropyl trimethoxyl silane (CPTMS): available from Aldrich company, purity〉97%.
3.3-chloropropyl trichloro-silane (CPTCS): available from Alfa company, purity〉97%.
4.3-chloropropyl dimethoxy-methyl silane (CPDMS): available from Aldrich company, purity〉99%.。
5.3-chloropropyl dimethylchlorosilane (CPCS): available from Aldrich company.
6.3-bromopropyl Trimethoxy silane (BPTMS): available from Aldrich company, purity〉97%.
7.3-bromopropyl trichlorine base silane (BPPCS): available from Aldrich company, purity〉98%.
8.3-iodine propyl trimethoxy silicane (IPTMS): available from Aldrich company, purity〉95%.
9. aluminium foil: available from Aldrich company, purity〉99.99%.
10. silicon sol: available from Aldrich company, LUDOX AS-40 SiO
2Content is 40%.
Embodiment 1:
(I) the surperficial matrix through functional modification of preparation:
The porous alumina ceramic matrix is put into the toluene solution (strength of solution is 0.2mol/L) that is dissolved with CPTMS, and reaction is 1 hour under 383K, thereby introduces the silane linker with chloropropyl at the porous alumina ceramic matrix surface.
(II) the synthetic liquid of preparation LTA type molecular screen membrane:
Take by weighing 22.22g NaOH and be dissolved in the 47.5g distilled water, add the 0.30g aluminium foil after the clarification, stir the solution that forms aluminium; Measure the 4.17g silicon sol and be added in the pre-heated 50g distilled water, fully stir; Pre-heated aluminum solutions is slowly added in the silicon sol, fully stir, solution at room temperature continues to stir 24h subsequently.Prepare at last liquid and comprise Na
2O, Al
2O
3, SiO
2And H
2O (is equivalent to contain and comprises NaAlO
2And Na
2SiO
3The sial presoma of aquo complex) and four mol ratio be 50:1:5:1000.
(III) preparation LTA type molecular screen membrane:
The matrix that the surface is modified is placed in the reactor of the synthetic liquid of LTA type molecular screen membrane that (II) is housed, utilize baking oven that reactor is heated to 333K, take out reaction solution at Hydrothermal Synthesis under this temperature after 24 hours, be cooled to room temperature, be washed with distilled water to neutrality, under the 383K temperature, dry product, thereby obtain LTA type molecular screen membrane.
LTA type molecular screen membrane morphology characterization:
The LTA type molecular sieve that embodiment 1 is made carries out surface and section SEM evaluation, and the photo that obtains respectively is shown in Fig. 1 and 2.Can be found out by Fig. 1 and 2, matrix surface generates the fine and close continuous LTA molecular sieve film of one deck.
LTA type molecular screen membrane forms to be identified:
The LTA type molecular screen membrane that the porous alumina ceramic that LTA zeolites product, embodiment 1 are made supports and porous alumina ceramic matrix carry out X-ray diffraction to be identified, respectively (a), (b), (c) of gained X-ray diffraction spectrogram such as Fig. 3.As seen from Figure 3, the LTA type molecular screen membrane that embodiment 1 makes is pure phase, does not have stray crystal to generate.
The gas separating property test of LTA type molecular screen membrane:
Adopt trifluoropropyl siloxane O type packing ring that the LTA molecular screen membrane for preparing is sealed on the membrane permeation pond, a side of film passes into H
2, CO
2, N
2, CH
4And C
3H
8Single-component gas perhaps passes into isopyknic H
2And CO
2, N
2, CH
4, C
3H
8Bi-component gas, the opposite side of film produces pressure reduction so that the power of gas-permeable to be provided by sweep gas in the film both sides, thereby estimates the gas separating property of the LTA molecular screen membrane film for preparing.The gas separating property test result of the molecular sieve that embodiment 1 makes as shown in Figure 4.Being shown by test result, is 293K and pressure reduction when being 1bar in temperature, the H of the LTA molecular screen membrane of embodiment 1
2/ CO
2, H
2/ N
2, H
2/ CH
4And H
2/ C
3H
8The separation factor of mixed gas is respectively 7.4,6.8, and 5.2 and 15.3, all be higher than corresponding Knudsen diffusion coefficient, have good separation selectivity.
The Knudsen diffusion coefficient of two component gases is the subduplicate inverses of two molecular weight gas among Fig. 4; The perfect gas separation factor is the ratio of single-component gas infiltration capacity; The mixed gas separation factor is the ratio of mixed gas infiltration capacity.
Embodiment 2-12:
Embodiment 2 to 12 adopts and embodiment 1 essentially identical step prepares LTA type molecular screen membrane, but the employed matrix kind of step (I), organosilane kind, the preparation liquid of step (II) forms, and step (III) type of heating, temperature and time are all different, and the parameter of each embodiment is listed in the nextpage table 1.
Because the surface of the LTA type molecular screen membrane that embodiment 2 to 12 makes and section SEM qualification result and X-ray diffraction spectrogram are very close with embodiment 1, for saving space, this paper does not show SEM and the XRD result of embodiment 2 to 12.
Embodiment 13(Comparative Examples):
Comparative Examples is directly to prepare LTA type molecular screen membrane on without the porous alumina ceramic matrix of functional modification, and the step (II) of namely directly carrying out embodiment 1 reaches (III), and its experiment parameter is also listed in the lower page table 1.
Table 1: embodiment experiment parameter
Molecular screen membrane thickness, film growing state, gas delivery experiment:
Following foundation as the aforementioned SEM identifies and the gas delivery experiment, and the permeation sepn performance tabulation of LTA type molecular screen membrane layer thickness, coating growth situation and the molecular screen membrane that each embodiment and Comparative Examples are made shows, and is as shown in table 2.
Table 2:
In sum, the inventive method does not need to introduce crystal seed layer at matrix, and the organosilane by the double functional group makes the sial presoma of synthetic LTA molecular screen membrane directly in matrix surface nucleation and growth under Hydrothermal Synthesis, therefore operates simple and easyly, is suitable for industry and amplifies.Moreover the prepared LTA type of the present invention molecular screen membrane is even compact, does not have stray crystal to generate, LTA type molecular screen membrane is actually used in H
2, N
2, CO
2And has good separation selectivity during the separation of the mixed gass such as low-carbon alkanes gas.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. the preparation method of a LTA type molecular screen membrane is characterized in that, described method comprises following steps:
(a) matrix that has a hydroxyl by the surface with have haloalkyl and can with the covalent bonding reaction of the organosilane of the active group of hydroxyl covalent bonding, thereby introduce the silane linker with haloalkyl at matrix surface, obtain the surface through the matrix of functional modification; And
(b) above-mentioned surface is contacted with the preparation liquid that contains for the synthesis of the sial presoma of LTA type molecular screen membrane through the matrix of functional modification, make the described haloalkyl that is arranged in the silane linker of matrix surface carry out the covalent bonding reaction at Hydrothermal Synthesis and sial presoma, thereby prepare LTA type molecular sieve rete at matrix surface, and therefore make LTA type molecular screen membrane, it comprise matrix, LTA type molecular sieve rete and be positioned at the two and with the silane linker that removes halogen of matrix and the equal covalent bonding of sieve membrane layer.
2. preparation method as claimed in claim 1, it is characterized in that, described organosilane comprises one or two or more kinds in 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl trichloro-silane, 3-chloropropyl dimethoxy-methyl silane, 3-chloropropyl dimethylchlorosilane, 3-bromopropyl Trimethoxy silane, 3-bromopropyl trichlorine base silane, the 3-iodine propyl trimethoxy silicane.
3. preparation method as claimed in claim 1 is characterized in that, described preparation liquid comprises Na
2O, Al
2O
3, SiO
2And H
2O, and described sial presoma comprises NaAlO
2And Na
2SiO
3Aquo complex.
4. preparation method as claimed in claim 3 is characterized in that, described Na
2O, Al
2O
3, SiO
2And H
2The mole ratio of O is (7.5-50): (1-2.5): (5-10): (300-1000).
5. preparation method as claimed in claim 1 is characterized in that, described matrix is one or two or more kinds in porous alumina ceramic, porous titanium dioxide ceramic, porous stainless steel disc, stainless (steel) wire, ptfe substrate, the glass substrate.
6. preparation method as claimed in claim 1 is characterized in that, the temperature of reaction of described step (a) is 353-393K.
7. preparation method as claimed in claim 1 is characterized in that, the temperature of reaction of described step (b) is 323-373K.
8. LTA type molecular screen membrane, it is characterized in that described molecular sieve comprise matrix, LTA type molecular sieve rete and be positioned at the two and with the silane linker that removes halogen of matrix and the equal covalent bonding of sieve membrane layer, and by obtaining such as arbitrary described preparation method among the claim 1-7.
9. molecular screen membrane as claimed in claim 8 is characterized in that, the thickness of described LTA type molecular sieve rete is between 2-5 μ m.
10. molecular screen membrane as claimed in claim 8 is characterized in that, described molecular screen membrane is for H
2, N
2, CO
2Reach the separation of the mixed gas more than two kinds in the low-carbon alkanes gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104525255A (en) * | 2014-12-23 | 2015-04-22 | 中国科学院过程工程研究所 | Preparation method for supporting ordered mesoporous molecular sieve SBA-15 on metal foam matrix |
| CN111921390A (en) * | 2020-07-15 | 2020-11-13 | 上海念诺膜技术有限公司 | Method for synthesizing compact LTA type molecular sieve membrane by covalent bonding hydrothermal method |
| CN111992050A (en) * | 2020-09-10 | 2020-11-27 | 南京惟新环保装备技术研究院有限公司 | Carrier surface modified hydrophilic molecular sieve membrane and preparation method thereof |
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| CN104525255A (en) * | 2014-12-23 | 2015-04-22 | 中国科学院过程工程研究所 | Preparation method for supporting ordered mesoporous molecular sieve SBA-15 on metal foam matrix |
| CN111921390A (en) * | 2020-07-15 | 2020-11-13 | 上海念诺膜技术有限公司 | Method for synthesizing compact LTA type molecular sieve membrane by covalent bonding hydrothermal method |
| CN111992050A (en) * | 2020-09-10 | 2020-11-27 | 南京惟新环保装备技术研究院有限公司 | Carrier surface modified hydrophilic molecular sieve membrane and preparation method thereof |
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| CN103058213B (en) | 2015-04-08 |
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