CN101343067B - Method for renovating molecular sieve membrane defection by means of liquid-liquid interfacial chemical liquid deposition - Google Patents
Method for renovating molecular sieve membrane defection by means of liquid-liquid interfacial chemical liquid deposition Download PDFInfo
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- CN101343067B CN101343067B CN200810151236XA CN200810151236A CN101343067B CN 101343067 B CN101343067 B CN 101343067B CN 200810151236X A CN200810151236X A CN 200810151236XA CN 200810151236 A CN200810151236 A CN 200810151236A CN 101343067 B CN101343067 B CN 101343067B
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Abstract
The invention discloses a method of restoring defects of molecular sieve film by making use of liquid-liquid interface chemical liquid deposition, comprising the following steps: (1) a silylation reaction solution is contacted with a side of the molecular sieve of the molecular sieve film to be restored and kept at atmospheric pressure; the other side of the film is fed with nitrogen, while the pressure is higher than atmospheric pressure; and the molecular sieve film which is covered by a layer of silicone is obtained after circumfluence, washing and drying; and (2) an organic silane solution is contacted with a side of the film which is covered by the layer of silicone, while the pressure is higher than the atmospheric pressure, so that the other side of the film is contacted with an alkaline catalyst aqueous solution, kept at the atmospheric pressure, reacted for 8 to 72 hours, washed and dried. Step (1) of the method not only protects the molecular sieve holes but also plays a role of surface chemical modification, so that the external surface of the molecular sieve is fully hydrophobic; and Step (2) results in that the opening of the defects of the film forms an oil-water interface, so that the organic silane takes the hydrolysis polycondensation reaction at the oil-water interface to form dense organic-inorganic silicon hybrid, so as to achieve the purpose of selectivelyrestoring the defects of the film.
Description
Technical field
The invention belongs to the maintenance technology of molecular screen membrane.Relate to a kind of selectivity and repair the method for molecular screen membrane defective, particularly relate to a kind of method of repairing the molecular screen membrane defective by the liquid-liquid interface chemical liquid deposition.
Background technology
Advantages such as that zeolite molecular sieve has is high temperature resistant, mechanical strength is high, anti-chemistry and bioerosion.As a kind of novel inorganic membrane material that development in recent years is got up, continuous and flawless molecular screen membrane possesses excellent molecule screening and shape selective catalysis performance, can be widely used in film and separate and the film catalytic process.The molecular screen membrane of having reported at present has types such as LTA, FAU, T, MFI and MOR.Wherein the molecular diameter of MFI type molecular sieve (ZSM-5, Sillicalite-1 and Metal-ZSM-5) aperture size and many essential industry raw materials is suitable, and MFI type molecular screen membrane application potential in processes such as the separation of dimethylbenzene homologue, ethanol-water mixture separation and hydro carbons partial oxidation is huge.Though laboratory scale zeolite molecular sieve film has been obtained certain progress, heavy industrialization is used also very rare.In the synthetic or use, often be accompanied by the formation of film defective at molecular screen membrane, hindered the practical application of molecular screen membrane.Therefore, how to eliminate the molecular screen membrane defective, the defective that forms in the particularly online reparation use is one of key content of present molecular screen membrane research and extension work.
According to the definition of IUPAC, the molecular screen membrane defective can be divided into big hole defect (〉 50nm), mesoporous defective (2nm～50nm) and micropore defective (＜2nm).Big hole defect refers generally to crack and pin hole, and mesoporous and micropore defective is often referred to the hole between the zeolite grain under hydrothermal synthesizing condition.Because the intrinsic character of zeolite molecular sieve film and the imperfection of synthetic technology, synthetic at present large tracts of land, ultra-thin and flawless molecular screen membrane are very difficult.Therefore, developing a kind of effective molecular screen membrane recovery technique, eliminate or reduce defective, significantly improve the separating property and the repeatability of film, is a kind of effective way.
According to bibliographical information, can existing molecular screen membrane defect-restoration method therefor be divided three classes i.e. carbon distribution coking method, face coat method and chemical vapour deposition technique (CVD) according to repair mechanisms.Existing molecular screen membrane restorative procedure only limits to repair micropore defective or mesoporous defective, and the raising of permselective property is a cost to reduce permeation flux.
People such as Yan [J Membr Sci, 123,95 (1997)] 1,3, soak the ZSM-5 molecular screen membrane in the 5-triisopropylbenzene (TIPB), high-temperature heat treatment is carried out the carbon distribution coking in air then.Because the molecular dimension (about 0.84nm) of TIPB is greater than ZSM-5 molecular sieve bore diameter (about 0.55nm), TIPB can't enter molecular sieve pore passage, thus after the carbon distribution coking shutoff intracrystalline pore of molecular screen membrane.Molecular screen membrane after the reparation in the time of 185 ℃ just/selectivity of iso-butane single-component gas infiltration is increased to 107 from 9.7.Yet the permeation flux of repairing caudacoria reduces significantly, and this method can only the repair-deficiency size less than the defective of 4nm.
For the face coat method, people such as Xomeritakis [Ind Eng Chem Res, 40,544, (2001)] be coated with the polymerization silica gel that last layer adds CTAB on MFI molecular screen membrane surface by being stained with the method for being coated with (dip-coating), dry back forms mesoporous silicon coating on the molecular screen membrane surface, with gases at high pressure the mesoporous silicon coating purging on surface is removed then, to improve the selectivity of film.Because molecular sieve pore passage is easily blocked, the film permeation flux significantly reduces.People such as Matsuda [J Membr Sci, 210,433, (2002)] adopt two kinds of silicone rubbers (KE45 and KE108) at room temperature to repair the molecular screen membrane defective.The concentration of silicone rubber solution less than 3% to guarantee shutoff film defective but do not cover molecular sieve pore passage.The infiltration evaporation experimental result shows, is that the separating property of the molecular screen membrane after the cost reparation is improved to reduce permeation flux significantly.
Chemical vapour deposition technique can be used for repairing inoranic membrane and organic film.People such as Nomura [Ind Eng Chem Res, 36,4217, (1997)] adopt TEOS/O
3Diffuse in reverse direction CVD technology has been repaired the defective of silicalite-1 molecular screen membrane.By the CVD technology, be the silicon source with TEOS, with O
3Be oxidant, form one deck amorphous silicon on the molecular screen membrane surface.Under the 288K condition, the molecular screen membrane after the reparation just/iso-butane separate to select the factor to be increased to 87.8 from 9.1.But this method can only be repaired SF
6Permeation flux is less than 10
-8Molm
-2s
-1Pa
-1The micropore defective.Equally, people such as McHenry (US Patent, 5,672,388,1997) diffuse to the defective aperture respectively by ozone and silicon compound oxidation reaction take place from the film both sides, and the amorphous silicon deposit that reaction generates is with the defective shutoff.Silicon compound both can be that the silicon compound of gas phase also can be the silicon compound of liquid phase, as hexamethyldisilane, tetramethoxy-silicane, tetraethoxysilane and silicone oil etc.Molecular screen membrane one pack system permselective property after the reparation is greatly improved.Yet the chemical vapour deposition technique complex process is repaired back molecular screen membrane flux and is significantly reduced, and the repairing condition harshness, is unsuitable for actual industrial process.
In addition, people such as Anthonis (US Patent, 6,074,457,2000) adopt at molecular screen membrane surface preparation one deck refractory material and repair the molecular screen membrane defective.Refractory masses is carbide or boride, silica and the titanium nitride of silicon normally, and thickness is generally between 1nm～1 μ m.Refractory masses both had been used for the repair membrane defective, had also improved the anti-wear performance of molecular screen membrane.But because the requirement of this restorative procedure repeats calcining under hot conditions, thereby very easily produce new defective.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, the process conditions gentleness is provided, simple a kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective of process makes the molecular screen membrane through repairing have higher separating property under the situation that keeps high permeating flux.
Technical scheme of the present invention is summarized as follows:
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective may further comprise the steps:
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying fully contacted Silanization reaction liquid with the molecular sieve side of described film and keeps normal pressure; Opposite side at described film feeds dry nitrogen or helium, makes its pressure be higher than normal pressure 0.5～2.5MPa; 0～150 ℃, back flow reaction 0.5～24 hour is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 1～3 hour, the covering of the film that organosilan solution and described step (1) are handled organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 0.2～2.0MPa, the opposite side that makes film and pH value are that the aqueous solution of 8～12 base catalyst fully contacts, pressure is normal pressure, at 0～60 ℃, reacts 8～72 hours, use acetone, ethanol and deionized water cleaning, drying successively;
Described Silanization reaction liquid is to comprise what at least a silane coupler and organic solvent were made into, and the molar content of silane coupler is 1%～30% in the described Silanization reaction liquid;
Described organosilan solution is to comprise what at least a organosilan and organic solvent were made into, and the molar content of organosilan is 0.5%～30% in the described organosilan solution.
Described step (1) is preferably: after molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying fully contacted Silanization reaction liquid with the molecular sieve side of described film and keeps normal pressure; Opposite side at described film feeds dry nitrogen or helium, makes its pressure be higher than normal pressure 1～2MPa; 10～50 ℃, back flow reaction 1～10 hour is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer.
The general structure of described silane coupler is:
R
1-Si-(L
1)
3
L wherein
1=OCH
3, OC
2H
5Or Cl; R
1=phenyl, C
1～C
22Straight chained alkyl or C
1～C
22Branched alkyl.
Silane coupler is preferred: octadecyl trichlorosilane or dodecyl trimethoxy silane.
The general structure of organosilan is:
X-R
2-Si-(L
2)
3
Wherein X=H, HS, CI, NH
2Or OH; R
2=OCH
2, OC
2H
4, OC
3H
6, OC
4H
8, C
6H
4, C
1～C
22Straight chained alkyl or C
1～C
22Branched alkyl; L
2=OCH
3, OC
2H
5, OC
3H
7, OC
4H
9Or Cl.
Described organosilan is preferred: methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, γ-r-chloropropyl trimethoxyl silane or γ-chloropropyl triethoxysilane.
In the described Silanization reaction liquid or organosilan solution in organic solvent be at least a water-fast linear paraffin, branched paraffin, aromatic hydrocarbons, chlorohydrocarbon or fluorohydrocarbon.
In the described Silanization reaction liquid or organosilan solution in organic solvent preferred: benzene, toluene, heptane or octane.
Described organosilan solution is that mol ratio is the γ-r-chloropropyl trimethoxyl silane of 1:1:30～100: ethyl orthosilicate: octane or mol ratio are the γ-chloropropyl triethoxysilane of 1:1:30～100: ethyl orthosilicate: octane.
Described base catalyst is NaOH, KOH, NH
4OH, (CH
3)
4NOH, (C
2H
5)
4NOH or (C
3H
7)
4NOH.
The present invention at first on film to be repaired preparation be used to protect the organosilicon molecular layer of molecular sieve pore passage, not only protected molecular sieve pore passage but also played the effect of surface chemical modification, make the molecular screen membrane outer surface hydrophobic fully; Make the aqueous solution of organosilan solution and base catalyst form oil-water interfaces by the controlling diaphragm pressure at both sides again at place, film defective aperture, make organosilan form fine and close organic-inorganic silicon hybrid, thereby reach the purpose of selectivity repair membrane defective at oil-water interfaces generation hydrolysis condensation reaction.
Description of drawings
Fig. 1. preparation is used to protect the device flow chart of the organosilicon molecular layer of molecular sieve pore passage on film to be repaired.1-nitrogen steel cylinder, 2-pressure-reducing valve, 3-membrane reactor, 4-pressure sensor, 5-pressure-regulating valve, 6-condenser.
Fig. 2. utilize liquid-liquid interface chemical deposition reaction to repair the device flow chart of molecular screen membrane.The 11-storage tank, 12-measuring pump, 3-membrane reactor, 14-pressure sensor, 15-pressure-regulating valve, 16, the 17-stop valve, 18-alkaline catalyst solution storage tank, 19-alkaline catalyst solution recycling can, 20-vavuum pump.
Fig. 3. ((a) is for before repairing to adopt method of the present invention to repair the infrared spectrogram of molecular screen membrane front and back; (b) for repairing the back).
Fig. 4. adopt the electron probing analysis in molecular screen membrane cross section after the method reparation of the present invention.
Fig. 5. adopt method of the present invention to repair the infiltration cell size analysis result of front and back molecular screen membrane.Fig. 5 a be the He permeability with relative vapour pressure between relation, Fig. 5 b is the relation between He permeability and the Kelvin diameter.
Initial concentration is the CO of 50% (mole) under Fig. 6 .300K condition
2/ N
2The system film is detained the influence figure of side stagnation pressure to the gas separating property of film before and after repairing.Fig. 6 a is that film is detained the influence of side stagnation pressure to separation factor, and Fig. 6 b is that film is detained the side stagnation pressure to CO
2The influence of permeation flux.
The specific embodiment
The present invention is further illustrated below in conjunction with the specific embodiment accompanying drawing.
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective may further comprise the steps: (seeing Fig. 1 and Fig. 2)
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
Zeolite molecular sieve film to be repaired cleans with hydrogen peroxide dipping, after 150 ℃ of dryings, zeolite molecular sieve film to be repaired is placed in the membrane reactor 3, Silanization reaction liquid is fully contacted with the molecular sieve side of film and keeps normal pressure; Opposite side at film feeds dry nitrogen, makes its pressure be higher than normal pressure 1MPa; 50 ℃, back flow reaction 10 hours is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer; The preparation of Silanization reaction liquid is: the dodecyl trimethoxy silane is dissolved in toluene, and the molar concentration of dodecyl trimethoxy silane is 15%;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 2 hours, the covering of the film that organosilan solution and step (1) are handled organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 2.0MPa, the opposite side that makes film and pH value are that 10 the NaOH aqueous solution fully contacts, and pressure is normal pressure, at 40 ℃, reacted 36 hours, use acetone, ethanol and deionized water cleaning, drying successively, the molecular screen membrane after promptly obtaining to repair; Organosilan solution is that γ-r-chloropropyl trimethoxyl silane, ethyl orthosilicate and the octane of mol ratio 1:1:50 is mixed and made into.
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective may further comprise the steps:
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After silicalite-1 molecular screen membrane to be repaired cleans with hydrogen peroxide dipping, 150 ℃ of dryings 10 hours, silicalite-1 molecular screen membrane to be repaired is installed in (see figure 1) in the membrane reactor, be that 5% dodecyl trimethoxy silane octane solution fully contacts with silicalite-1 molecular sieve side and keeps normal pressure with the 10ml molar concentration, the opposite side of film feeds dry nitrogen makes its pressure be higher than normal pressure 1Mpa, be under 20 ℃ the condition in temperature, after the back flow reaction 4 hours, be warming up to 110 ℃ and continue reaction 8 hours; Use acetone, ethanol and deionized water cleaning, drying successively, obtain to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 2 hours, with mol ratio is γ-chloropropyl triethoxysilane of 1:1:70: ethyl orthosilicate: the organosilan solution that octane is made into adds storage tank 11, by measuring pump 12 organosilan solution is imported in the membrane reactor 3, make organosilan solution and covered organosilicon molecular layer one side and fully contact and circulate, pressure is higher than normal pressure 0.25MPa (see figure 2), open stop valve 16,17, the pH value is that 9 ammoniacal liquor chloride buffer solution is introduced membrane reactor and fully contacted with the opposite side of film from alkaline catalyst solution storage tank 18, and pressure keeps normal pressure; Be under 25 ℃ the condition, to react after 48 hours in temperature, clean and vacuum drying with 100mL acetone, ethanol and deionized water successively, be used for after the oven dry characterizing and CO
2/ N
2Mist separates.
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, 150 ℃ of dryings 10 hours were that 5% octadecyl trichlorosilane octane solution fully contacts with the molecular sieve side of film and keeps normal pressure with the 10ml molar concentration; Opposite side at film feeds dry nitrogen, makes its pressure be higher than normal pressure 1MPa; 20 ℃, back flow reaction 4 hours is warming up to 110 ℃ and continues reaction 8 hours; Use acetone, ethanol and deionized water cleaning, drying successively, obtain to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
Step is with embodiment 2.
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
Step is with embodiment 2;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 2 hours, with mol ratio is γ-r-chloropropyl trimethoxyl silane of 1:1:70: ethyl orthosilicate: the covering of the film that the organosilan solution that octane is made into and step (1) are handled organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 0.2～2.0MPa, the opposite side that makes film and pH value are that 9 ammoniacal liquor chloride buffer solution fully contacts, pressure is normal pressure, at 25 ℃, reacted 48 hours, use acetone, ethanol and deionized water cleaning, drying successively; Be used for after the drying characterizing and CO
2/ N
2Mist separates.
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective, may further comprise the steps: (1) prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage on film to be repaired
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying was 1% CH with molar content
3Si (OCH
3)
3Monochlorethane solution fully contact with the molecular sieve side of described film and keep normal pressure; Opposite side at described film feeds dry helium, makes its pressure be higher than normal pressure 0.5MPa; 150 ℃, back flow reaction 0.5 hour is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer.
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 1 hour, with mol ratio is γ-r-chloropropyl trimethoxyl silane of 1:1:30: ethyl orthosilicate: the covering of the organosilan solution that octane is made into (present embodiment also can select for use γ-chloropropyl triethoxysilane to substitute γ-r-chloropropyl trimethoxyl silane form new embodiment) and the film of described step (1) processing organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 0.2MPa, the opposite side that makes film and pH value are that the aqueous solution of 10 NaOH fully contacts, pressure is normal pressure, at 0 ℃, reacted 72 hours, use acetone successively, ethanol and deionized water cleaning, drying.
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective may further comprise the steps:
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying was 30% C with molar content
6H
5Si (OCH
3)
3Toluene solution fully contact with the molecular sieve side of described film and keep normal pressure; Opposite side at described film feeds dry helium, makes its pressure be higher than normal pressure 2.5MPa; 0 ℃, back flow reaction 24 hours is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 3 hours, with mol ratio is γ-r-chloropropyl trimethoxyl silane of 1:1:100: ethyl orthosilicate: the covering of the organosilan solution that octane is made into (present embodiment also can select for use γ-chloropropyl triethoxysilane to substitute γ-r-chloropropyl trimethoxyl silane form new embodiment) and the film of described step (1) processing organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 2.0MPa, the opposite side that makes film and pH value are that 9 the KOH aqueous solution fully contacts, pressure is normal pressure, at 60 ℃, reacted 8 hours, use acetone successively, ethanol and deionized water cleaning, drying.
Embodiment 7
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective may further comprise the steps:
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying was 15% C with molar content
22H
45Si (OC
2H
5)
3Octane solution fully contact with the molecular sieve side of described film and keep normal pressure; Opposite side at described film feeds dry nitrogen, makes its pressure be higher than normal pressure 1MPa; 40 ℃, back flow reaction 10 hours is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 2 hours, with molar content be 0.5% methyl silicate n-heptane solution (methyl silicate that also can select ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate to substitute in the present embodiment is formed new embodiment) and the film of described step (1) processing covering organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 1.0MPa, and making the opposite side of film and pH value is 12 NH
4The OH aqueous solution fully contacts, and pressure is normal pressure, at 20 ℃, reacts 36 hours, uses acetone, ethanol and deionized water cleaning, drying successively.
Embodiment 8
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective may further comprise the steps:
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying was 20% C with molar content
16H
33Si (OCH
3)
3Toluene solution fully contact with the molecular sieve side of described film and keep normal pressure; Opposite side at described film feeds dry helium, makes its pressure be higher than normal pressure 2MPa; 100 ℃, back flow reaction 2 hours is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 2 hours is 30%HSC with molar content
2H
4SiCl
3The film handled of chloroethanes solution and described step (1) covering organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 0.5MPa, making the opposite side of film and pH value is 8 (CH
3)
4The NOH aqueous solution fully contacts, and pressure is normal pressure, at 15 ℃, reacts 20 hours, uses acetone, ethanol and deionized water cleaning, drying successively.
Embodiment 9
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective, may further comprise the steps: (1) prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage on film to be repaired
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying was 10% C with molar content
14H
29SiCl
3Toluene solution fully contact with the molecular sieve side of described film and keep normal pressure; Opposite side at described film feeds dry helium, makes its pressure be higher than normal pressure 2MPa; 100 ℃, back flow reaction 2 hours is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 2 hours is 20%H with molar content
2NC
6H
4Si (OCH
3)
3The film handled of benzole soln and described step (1) covering organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 0.5
MPa, making the opposite side of film and pH value is 8 (C
2H
5)
4The NOH aqueous solution fully contacts, and pressure is normal pressure, at 40 ℃, reacts 42 hours, uses acetone, ethanol and deionized water cleaning, drying successively.
A kind of method by liquid-liquid interface chemical liquid deposition reparation molecular screen membrane defective may further comprise the steps:
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying was 12% C with molar content
6H
5Si (OCH
3)
3Dichloroethane solution fully contact with the molecular sieve side of described film and keep normal pressure; Opposite side at described film feeds dry helium, makes its pressure be higher than normal pressure 2MPa; 100 ℃, back flow reaction 2 hours is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 2 hours is 10%HO with molar content
2CH
2Si (OCH
3)
3The film handled of toluene solution and described step (1) covering organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 0.5MPa, making the opposite side of film and pH value is 8 (C
3H
7)
4The NOH aqueous solution fully contacts, and pressure is normal pressure, at 50 ℃, reacts 12 hours, uses acetone, ethanol and deionized water cleaning, drying successively.
Molecular screen membrane CO before and after repairing
2/ N
2The result that mist separates.
Annotate: CO
2/ N
2Gas separating experiment condition is 300K, △ P=250KPa.
Adopt infiltration porosimetry (permporometry) and CO
2/ N
2The molecular screen membrane that bi-component gas separates repairing front and back characterizes, and experimental result shows, uses the inventive method that the silicalite-1 molecular screen membrane is repaired, and the film defective can be from being decreased to below the 1nm CO more than the preprosthetic 70nm
2/ N
2Separation factor from preprosthetic 1 bring up to after the reparation more than 30, and CO under the isobaric condition
2Permeation flux only be reduced to 4/5ths of repair membrane not.This shows effectively shutoff molecular screen membrane defective and can not stop up molecular sieve pore passage of organic-inorganic silicon hybrid that oil-water interfaces form.
Compare with the present both at home and abroad molecular screen membrane restorative procedure of report, the present invention is based on the liquid deposition of liquid-liquid interface selective chemical, both protected molecular sieve pore passage, effectively filled out shutoff again greater than the molecular screen membrane defective of 70nm. The separating property of repairing rear molecular screen membrane is significantly improved, and permeation flux only reduce by 20%. Process conditions gentleness of the present invention, easy and simple to handle, repeatability is high, is suitable for industry and amplifies.
Claims (7)
1. repair the method for molecular screen membrane defective by the liquid-liquid interface chemical liquid deposition for one kind, it is characterized in that may further comprise the steps:
(1) on film to be repaired, prepares the organosilicon molecular layer that is used to protect molecular sieve pore passage
After molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying fully contacted Silanization reaction liquid with the molecular sieve side of described film and keeps normal pressure; Opposite side at described film feeds dry nitrogen or helium, makes its pressure be higher than normal pressure 0.5～2.5MPa; 0～150 ℃, back flow reaction 0.5～24 hour is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer;
(2) utilize liquid-liquid interface chemical deposition reaction to repair molecular screen membrane
The film vacuum exhaust that step (1) is handled 1～3 hour, the covering of the film that organosilan solution and described step (1) are handled organosilicon molecular layer one side fully contact, pressure is higher than normal pressure 0.2～2.0MPa, the opposite side that makes film and pH value are that the aqueous solution of 8～12 base catalyst fully contacts, pressure is normal pressure, at 0～60 ℃, reacts 8～72 hours, use acetone, ethanol and deionized water cleaning, drying successively;
Described Silanization reaction liquid is to comprise what at least a silane coupler and organic solvent were made into, and the molar content of silane coupler is 1%～30% in the described Silanization reaction liquid;
Described organosilan solution is to comprise what at least a organosilan and organic solvent were made into, and the molar content of organosilan is 0.5%～30% in the described organosilan solution;
The general structure of described silane coupler is:
R
1-Si-(L
1)
3
L wherein
1=OCH
3, OC
2H
5Or Cl; R
1=phenyl, C
1～C
22Straight chained alkyl or C
1～C
22Branched alkyl;
The general structure of described organosilan is:
X-R
2-Si-(L
2)
3
Wherein X=H, HS, Cl, NH
2Or OH; R
2=OCH
2, OC
2H
4, OC
3H
6, OC
4H
8, C
6H
4, C
1～C
22Straight chained alkyl or C
1～C
22Branched alkyl; L
2=OCH
3, OC
2H
5, OC
3H
7, OC
4H
9Or Cl;
Described base catalyst is NaOH, KOH, NH
4OH, (CH
3)
4NOH, (C
2H
5)
4NOH or (C
3H
7)
4NOH.
2. method according to claim 1 is characterized in that described step (1) is: after molecular screen membrane to be repaired cleaned with hydrogen peroxide dipping, drying fully contacted Silanization reaction liquid with the molecular sieve side of described film and keeps normal pressure; Opposite side at described film feeds dry nitrogen or helium, makes its pressure be higher than normal pressure 1～2MPa; 10～50 ℃, back flow reaction 1～10 hour is used acetone, ethanol and deionized water cleaning, drying successively, obtains to have covered the molecular screen membrane of organosilicon molecular layer.
3. method according to claim 1 is characterized in that described silane coupler is octadecyl trichlorosilane or dodecyl trimethoxy silane.
4. method according to claim 1 is characterized in that described organosilan is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, γ-r-chloropropyl trimethoxyl silane or γ-chloropropyl triethoxysilane.
5. method according to claim 1, it is characterized in that in the described Silanization reaction liquid or organosilan solution in organic solvent be at least a water-fast linear paraffin, branched paraffin, aromatic hydrocarbons, chlorohydrocarbon or fluorohydrocarbon.
6. method according to claim 5, it is characterized in that in the described Silanization reaction liquid or organosilan solution in organic solvent be benzene, toluene, heptane or octane.
7. method according to claim 1, it is characterized in that described organosilan solution is that mol ratio is γ-r-chloropropyl trimethoxyl silane of 1: 1: 30～100: ethyl orthosilicate: octane or mol ratio are γ-chloropropyl triethoxysilane of 1: 1: 30～100: ethyl orthosilicate: octane.
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| CN200810151236XA CN101343067B (en) | 2008-09-04 | 2008-09-04 | Method for renovating molecular sieve membrane defection by means of liquid-liquid interfacial chemical liquid deposition |
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| CN101874990B (en) * | 2009-11-16 | 2012-08-29 | 南京工业大学 | Repair method of intergranular pore channel of molecular sieve membrane |
| KR102017483B1 (en) | 2012-02-24 | 2019-09-03 | 미쯔비시 케미컬 주식회사 | Porous support-zeolite membrane composite |
| CN103801200B (en) * | 2012-11-05 | 2016-06-29 | 北京航空航天大学 | A kind of preparation method of high flux antipollution inoranic membrane |
| CN103551040B (en) * | 2013-11-15 | 2015-06-24 | 中国海洋石油总公司 | Online repairing method of NaA molecular sieve membrane |
| CN109499390A (en) * | 2018-12-14 | 2019-03-22 | 黄山学院 | A method of quickly repairing inoranic membrane defect using Microwave-assisted firing |
| CN111346516B (en) * | 2020-03-12 | 2022-06-24 | 江西师范大学 | Modification method of T-shaped molecular sieve membrane, modified T-shaped molecular sieve membrane and application thereof |
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