CN101318665B - Method for preparing high-performance Y type molecular sieve film and application of the same in organic mixture separation - Google Patents
Method for preparing high-performance Y type molecular sieve film and application of the same in organic mixture separation Download PDFInfo
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- CN101318665B CN101318665B CN2008101069333A CN200810106933A CN101318665B CN 101318665 B CN101318665 B CN 101318665B CN 2008101069333 A CN2008101069333 A CN 2008101069333A CN 200810106933 A CN200810106933 A CN 200810106933A CN 101318665 B CN101318665 B CN 101318665B
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Abstract
The invention provides a method for preparing a high-performance Y-type molecular sieve membrane and an application to the separation of organic mixture. The method is characterized in that a new high-temperature closed hydro-thermal synthesis reaction method is adopted, a layer of dense NaY-type molecular sieve membrane forms on the surfaces of three porous tubular support body. The synthetic time of preparation process is short, and the process of the membrane forming is simple. The membrane prepared by the method has fewer defects, the synthesized NaY-type molecular sieve membrane is used in the separation of organic mixtures by adopting a self-control permeating and vaporizing device, the process of the separation is simple and is easy to be operated and controlled, the separating property is good, the Y-type molecular sieve membrane has high permeation flux and high separation factor while the Y-type molecular sieve membrane is applied to methanol/ methyl tert-butyl ether, ethanol/ethyl tertiary butyl ether and benzene/cyclohexane, the NaY-type molecular sieve membrane particularly synthesized by stainless steel support body has extremely high permeation flux.
Description
Technical field
The invention provides the application of a kind of high-performance Y type molecular sieve film preparation methods and the separation in organic admixture thereof, belong to inorganic material permeability and separation field.
Background technology
Membrane separation technique is one of focus of recent research, and its development speed is very fast.Because it is more economical that film separates more traditional separating technology, and have desirable Energy Efficiency Ratio, membrane separation technique is widely used in water treatment field in chemical industry, oil, environment and food, the electronics industry by the worker.In the past few decades, various organic films are used for practicability technical fields such as micro-filtration, nanofiltration, dialysis, counter-infiltration, infiltration evaporation, steam infiltration and gas separate with inoranic membrane.
Infiltration evaporation and steam infiltration technology are the important means of industrial separation and azeotropic azeotropic mixture.Use this technology and deviate from the important component part that water in organic matter thing or the mixed solvent has become application of membrane separation technology.And the organic mixture that utilizes infiltration evaporation and steam permeability and separation mainly contains a few class mixtures such as alcohol-ether mixture, aromatic hydrocarbon isomers, aromatic hydrocarbon and alkane.
For example: the separation of alcohol, ether mixture mainly is separating of methyl alcohol/methyl tertiary butyl ether(MTBE) and ethanol/ethyl tert-butyl ether (ETBE).Methyl tertiary butyl ether(MTBE) (MTBE) and ethyl tert-butyl ether (ETBE) (ETBE) mainly are used as the additive of unleaded gas.Though various countries are gradually reducing the consumption of MTBE as gasoline additive for the consideration of environmental protection, MTBE is the important source material of many chemical products, and consumption is very big.General excessive methyl alcohol or the ethanol of using is as reaction raw materials in the production process of MTBE and ETBE.The at present industrial recovery methyl alcohol that generally adopts and the method for ethanol are rectification method, the method energy consumption height and process complexity.1988, U.S. Air Product ﹠amp; Chemical Inc (patent US 4774365) has reported two kinds of new technologies that combine with distillation based on the infiltration evaporation of cellulose acetate membrane at first, and this technology is used for the separation of methyl alcohol/MTBE mixture, compares energy-conservation 30% with traditional handicraft.US 5238573 has developed a kind of perfluoro alkane polymer Nafion 117 films, is applied to 30 ℃, and the permeation flux in methyl alcohol/MTBE (5.3/94.5wt%) system is 0.1895kg/m
2H and separation factor are 25.
In addition, the infiltration vaporization separation film that is used to separate benzene/cyclohexane also receives much attention, and extraordinary application prospect is arranged.Kuskabae etc. (J.Membr.Sci., 1998, Vol 149, No.1, P 29) adopt polyurethane colloidal sol to be coated on α-Al
2O
3Made the macromolecule-inorganic hybridized film on the film, the separation factor that this film separates benzene/cyclohexane is 19, and total flux is 3 * 10
-5Kg/m
2H.Yang etc. (J.Membr.Sci., 2005, Vol 249, P 33) are respectively 1.6kg/m with the synthetic copolyimide film that includes crown ether of DsDA, DABC and DDBT to the permeation flux and the separation factor of 70 ℃ of benzene/cyclohexanes (60/40wt%)
2H and 28.
At present, existing multiple infiltrating and vaporizing membrane separates above two class organic mixtures.But majority is an organic polymer films.The not high or poor selectivity of the permeation flux of these films, and polymeric membrane is high temperature resistant and solvent resistance is relatively poor, and mechanical strength is also bad.
Molecular screen membrane is nearly ten years a kind of novel microporous inoranic membranes that grow up, because of it has good whole, can reach high flux, high selectivity, heat-resisting, solvent-proof requirement, than organic film better separating property is arranged, thereby be subject to people's attention, it is with the fastest developing speed to become the film field, also is one of the most promising technology.
For molecular screen membrane, because the aperture of its rete mesolite crystal mostly is the Ethylmercurichlorendimide level, thereby they are very suitable for the separation with mixture, and as membrane reactor.Most screening character that are based on the molecule sieve aperture of separating, its absorption and desorption characteristics and catalytic property are set up.
The molecular screen material that can prepare film forming comprises Silicalite, ZSM-5, faujasite (Faujasite), A type zeolite, T type zeolite and modenite etc.These zeolite molecular sieves are extensively in a lot of separation and catalytic process.According to the application purpose of zeolite molecular sieve, select different synthetic methods.Wherein hydro-thermal is synthetic is one of the method for molecular screen membrane for preparing the most commonly used.Yet molecular screen membrane does not have enough mechanical strengths, so film itself can not use separately.Generally be that molecular screen membrane is synthesized on the tabular or tubular support such as stainless steel in porous, aluminium oxide, mullite.
In the separation of liquid mixture, the A type molecular sieve film has very strong hydrophily, shows the excellent permeation performance in removing organic matter during water.The MFI film is that (for example ZSM-5 silicalite-1), has higher selectivity to organic matter to the hydrophobic type film, is fit to the separation of organic matter/water.The hydrophily of Faujasite type (X type, Y type) molecular screen membrane than the A type molecular sieve film a little less than, but this types of molecules sieve aperture road is bigger, and has good selecting property for unsaturated aromatic hydrocarbon, aliphatic hydrocarbon.
Adopting proportioning among the patent JP8257301 is SiO
2/ Al
2O
3=5～15, Na
2O/SiO
2=0.5～2, H
2O/Na
2The synthetic liquid of O=50～120 is formed, colloidal sol digestion time 6～24h, and 100～150 ℃ of crystallization 4～10h obtain NaY type molecular screen membrane on porous carrier.The film of preparation is to alcohol/water, and alcohol/cyclohexane has separating power preferably.
Patent JP8213004 as crystal seed, has synthesized NaY type molecular screen membrane with NaX, synthetic 6～24h under 90 ℃ hydrothermal condition, and optimizing generated time is 24 hours, uses proportioning to be SiO
2: Al
2O
3: Na
2O: H
2O=10: 1: 14: 798 synthetic liquid, the NaY type molecular screen membrane that makes is at separation of C O
2/ N
2During the system mist, good selectivity and flux have been shown.Use tubulose and tabular porous Alpha-alumina to be supporter in this patent, because the tubular support body diameter that is adopted only is 2.8 millimeters, 1.0 millimeters of internal diameters, surface average pore size 150 nanometers, separation for liquid mixture is restricted, and this supporter mechanical strength is very low, and involves great expense, and is unfavorable for suitability for industrialized production.The effective film area of same tabular supporter is little, with membrane module be connected, seal the difficulty.In addition, adopt X type (Si/Al=1.0～1.5) molecular sieve to be unfavorable for preparing the high Y type of framework of molecular sieve silica alumina ratio (Si/Al=1.5～3.0) molecular screen membrane as crystal seed.Patent US 20070110649 is equally by Kyushu University's application, and they adopt synthetic method identical with patent JP8213004 and similar supporter to prepare y-type zeolite membrane in this patent, and different is to adopt SiO
2: Al
2O
3: Na
2O: H
2O=12.8: 1: 17: 975 initial gel.The gas separating property of gained film is better, can anti-nearly 400 ℃ high temperature.
Patent CN 1294944A, CN 1285234A and CN 1112232C have described the synthetic of X type molecular screen membrane.These three patents are China PetroChemical Corporation and apply for.CN 1294944A, CN1285234A synthesize X type molecular screen membrane on porous carrier, CN 1112232C passes through the method for plug-hole, modification and high temperature carbon deposit to reducing the defective that exists in the X type molecular screen membrane.As a whole, the synthetic method of three patent employings all has low temperature crystallized (80～105 ℃), the characteristics of generated time long (24～69 hours).
Patent CN 100344352C, the employing proportioning is SiO
2/ Al
2O
3=3.85～4.2, Na
2O/SiO
2=1.2～1.5, H
2O/Na
2The synthetic liquid of O=55 is formed, and the employing earthenware is a supporter, and low-temperature hydrothermal (95～105 ℃) reaction 20～48 hours makes X type molecular screen membrane.Film after ion-exchange can be used for separating of benzene and nitrogen blending ingredients
Existing periodical literature (as Ind.Eng.Chem.Res., 2005, Vol 44, P 937, Ind.Eng.Chem.Res., 2005, Vol 44, and P 226, Sep.Purif.Technol., 2001, Vol 25, and P 261, Microporous Mesoporous Mater., 2002, Vol 54, and P 27, Ind.Eng.Chem.Res., 1997, Vol 36, P 649 etc.) in, the preparation of y-type zeolite membrane is all carried out under lower temperature (80～100 ℃), perhaps adopts the method for organic formwork agent synthetic.These preparation methods or good duration, or adopt repeatedly synthetic or the agent of interpolation template, the operating process complexity.And researcher's majority all is that the gas separating property of y-type zeolite membrane is investigated, as: titanium dioxide carbon/nitrogen gas, alkane isomers, C
nUnsaturated hydrocarbons/C
nThe separation of unsaturated hydrocarbons etc.To liquid mixture is arranged, particularly considerably less to binary organic component SEPARATING PROCESS, its result can not be satisfactory.In addition, great majority relate to the supporter that is adopted in the patent of Y zeolite film preparation and the document and are not suitable for suitability for industrialized production.
Domestic research for y-type zeolite membrane is considerably less, does not also have patent in this respect at present.
The present invention adopts the high temperature hydrothermal synthesizing condition to prepare the Y molecular sieve film, has improved the crystal structure degree and has shortened generated time, has increased the stability of film under the high-temperature operation condition.And preparation flow is very simple, quick.The supporter mechanical strength height that is adopted is suitable for commercial Application.Membrane surface molecule sieve crystal growth synthetic under the optimal conditions is good, and defective is considerably less.The Y molecular sieve film of gained has good separation selectivity to the organic matter mixed system.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of high-performance Y type molecular sieve film and the application that separates at organic mixture thereof.The present invention is optimized composition of raw materials, the synthesis condition in the preparation of NaY type molecular screen membrane, by the high-temperature water thermal synthesis, has shortened the generated time of film.Utilize this method on porous supporting body, to synthesize high-purity, the continuous molecular screen membrane of growth, and have generated time weak point, preparation process characteristic of simple.This molecular screen membrane can be realized methyl alcohol/methyl tertiary butyl ether(MTBE), ethanol/ethyl tert-butyl ether (ETBE), and benzene/cyclohexane organic mixture high selectivity is separated.
The preparation method of NaY type molecular screen membrane of the present invention is as follows:
5) the aluminium source is dissolved in sodium hydroxide solution, stirring state adds silicon source, preparation raw material liquid SiO down then
2-Na
2O-Al
2O
3-H
2The O system, the each component mol ratio is:
SiO
2/Al
2O
3＝11～28，
Na
2O/SiO
2＝0.5～2.5，
H
2O/Na
2O＝25～80.
6) continue to stir 2～6 hours, placed airtight polytetrafluoroethylcontainer container room temperature then still aging 0～24 hour.
7) colloidal sol for preparing adds in the stainless steel cauldron, and the tubular type porous supporting body of precoating kind is vertically inserted in the colloidal sol, and the colloidal sol liquid level needs the submergence supporter.90～150 ℃ of temperature are synthetic, 4.5～12.0 hours hydro-thermal reaction time; This supporter is tubular type porous mullite or stainless steel.
8) take out flush away surface alkali lye, washed with de-ionized water 24 hours, oven dry after reaction is finished.
Among the present invention, the supporter average pore size is 0.1～10 μ m, supporter porosity 30%～60%; External diameter of pipe 8～the 15mm of supporter, supporter thickness of pipe wall 1～3mm.
There are silica flour, Ludox and sodium metasilicate in the silicon source that the inventive method material liquid adopts.There are aluminium hydroxide, sodium metaaluminate in the aluminium source of adopting.The alkali that adopts is NaOH.
The hydro-thermal reaction optimum condition is among the present invention: during 110 ℃ of temperature, and 4.5～6.0 hours reaction time; During 100 ℃ of temperature, 6.0～12.0 hours reaction time.
The NaY type molecular screen membrane average thickness that synthesizes is at 20～30 μ m.Coating growth is good, continuous and be evenly distributed defectives such as free of pinholes, crack.
The present invention adopts water/organic matter and organic matter/organic admixture to characterize the performance of synthetic film.Water/the organic matter that adopts is the moisture water/alcohol mixture of 10wt% that is, operating temperature is 75 ℃.Because this system is simple to operate and toxicity is little, in the synthetic optimizing process of film, adopt this system characterization of membrane, instruct the optimization of film by permeation data.
Organic matter/organic admixture the system that adopts has:
Material liquid 1: the mass fraction that contains methyl alcohol is the methyl alcohol of 10wt%/methyl tertbutyl ether mixture, and operating temperature is 50 ℃.
Material liquid 2: the mass fraction that contains ethanol is the ethanol of 10wt%/ethyl tert-butyl ether mixture, and operating temperature is 50 ℃.
Material liquid 3: the mass fraction that contains benzene is the benzene/cyclohexane mixture of 10wt%, and operating temperature is 75 ℃.
Description of drawings
Fig. 1 is the installation drawing of the infiltration evaporation performance of the synthetic NaY type molecular screen membrane of detection.
Fig. 2 is at the NaY type molecular screen membrane surface Electronic Speculum figure that porous mullite supporter outer surface forms.
Fig. 3 is the NaY type molecular screen membrane section Electronic Speculum figure that forms at porous mullite supporter outer surface.
Fig. 4 is X-ray diffraction (XRD) comparison diagram of synthetic film under NaY type molecular sieve crystal seed, porous mullite supporter and the different temperatures.
In order to further describe the present invention, provided several concrete case study on implementation below, but patent right is not limited to these examples.
Specific embodiment
Adopting modulus is that 3.2 waterglass is the silicon source, and aluminium hydroxide is the aluminium source, and NaOH and deionized water are synthetic liquid raw material.
Adopt Japanese Nikkato Co., Ltd. system porous mullite pipe as the synthetic matrix of film, mullite consists of 67wt%Al
2O
3And 33wt%SiO
2Supporter applies one deck NaY type molecular sieve crystal seed after 800 order sand paperings and ultrasonic cleaning.
Aluminium hydroxide and NaOH are dissolved in deionized water, and adding waterglass formation mol ratio under stirring condition is 18Na
2O: 1Al
2O
3: 20SiO
2: 1260H
2The mixed liquor of O continues to stir 2 hours colloidal sol.This colloidal sol was placed airtight polytetrafluoroethylcontainer container at room temperature still aging 12 hours.Colloidal sol after the ageing is poured in the airtight stainless steel cauldron, and the supporter that will scribble NaY molecular sieve crystal seed in advance vertically puts into reactor, and guarantees that the colloidal sol liquid level is higher than supporter.And inserted in 100 ℃ the baking oven reaction 8 hours.
Synthetic film is with washing repeatedly with deionized water earlier, and the alkali lye to adsorb in the amorphous substance that washes film surface and inwall and the supporter continued to wash 24 hours with deionized water then, film under 100 ℃ drying 12 hours with standby.
The infiltration evaporation performance of synthetic film is to measure by device shown in Figure 1.This device comprises raw material flow container 1; Feed pump 2; Preheater 3; Temperature sensor 4; Membrane module 5; Condenser 6; Program control baking oven 7; Threeway method 8; Cold-trap 9; Vavuum pump 10; Vacuum meter 11
The film pipe is placed in the tubular type stainless steel mould, with the seal with elastometic washer of O shape.This mould places oven environment, the flow through outer surface of molecular screen membrane of feeding liquid.This tubular membrane inner chamber connects vacuum plant.The admixture of gas of infiltration is collected in the cold-trap by liquid nitrogen condensation.Adopt infiltration evaporation to detect infiltration evaporation flux, the separation that can directly obtain film, thus direct evaluated for film performance.
The infiltration evaporation performance of film is represented by permeation flux J and two parameters of separation α.Infiltration is by the material gross mass of the film of unit are in the permeation flux J representation unit time.See through quality/(unit interval * membrane area) of thing in the J=unit interval, unit is kg/m
2H; Separation α is used for the height of evaluated for film separative efficiency, α=(Y
A/ Y
B)/(X
A/ X
B), Y wherein
AWith Y
BBe illustrated respectively in the mass concentration of A and two kinds of components of B in the penetrant, X
AWith X
BBe illustrated respectively in the mass percent concentration of A and two kinds of components of B in the material liquid.The content employing type gas chromatographic detection of component A, B.
Synthetic film is applied to 75 ℃, the infiltration evaporation of water/ethanol (10/90wt%) system.Table 1 has shown the infiltration evaporation performance of the NaY type molecular screen membrane for preparing under the different condition.
Embodiment 2:
Synthetic ratio is identical with embodiment 1 with preparation process.Different is that crystallization temperature is increased to 110 ℃.Synthetic film is investigated the infiltration evaporation performance of film after treatment.Performance is as shown in table 1 as a result for it.
Embodiment 3:
Synthetic ratio is identical with embodiment 1 with preparation process.Different is that crystallization temperature is increased to 120 ℃, and generated time is reduced to 5 hours.Synthetic film is investigated the infiltration evaporation performance of film after treatment.Performance is as shown in table 1 as a result for it.
Supporter before synthetic, effective XRD of film and SEM instrument after synthetic are characterized, and XRD be day island proper Tianjin (SHIMADZU) XRD-6100 of company, and SEM is the JSM-6350 of company of NEC (JEOL).
Fig. 2 has shown the surface microstructure of NaY type molecular screen membrane synthetic on the porous mullite supporter.Supporting body surface is covered by one deck NaY type molecular sieve crystal, staggered, the closely growth of molecular sieve crystal
Fig. 3 has shown the cross-section morphology of the NaY type molecular screen membrane of synthetic film on mullite supports.As seen from the figure, at the porous supporting body outer surface fine and close continuously molecular sieve rete of one deck of having grown, have more fine and close intermediate layer between film top layer and the supporter, the rete gross thickness is about 20～30 μ m.
Fig. 4 is X-ray diffraction (XRD) comparison diagram of porous mullite supporter, synthetic NaY type molecular screen membrane, NaY type molecular sieve crystal.As shown in the figure, synthetic film has tangible NaY type molecular sieve crystal seed characteristic peak, the outer surface that the shows porous supporting body continuous NaY molecular sieve crystal of one deck of having grown.
Embodiment 4:
Synthetic ratio is identical with embodiment 1 with preparation process.Crystallization temperature is 130 ℃, and generated time is 5 hours.Synthetic film is investigated the infiltration evaporation performance of film after treatment in system.Performance is as shown in table 1 as a result for it.
Embodiment 5:
Changing synthetic is 18Na with the colloidal sol proportioning
2O: 1Al
2O
3: 20SiO
2: 1800H
2O, preparation process is identical with embodiment 1.Crystallization condition is a crystallization 5 hours under 120 ℃ of hydrothermal conditions.Synthetic film is as shown in table 1 to the infiltration evaporation performance of water/ethanol (10/90wt%) system.
Embodiment 6:
Changing synthetic is 36Na with the colloidal sol proportioning
2O: 1Al
2O
3: 40SiO
2: 2520H
2O, preparation process is identical with embodiment 1.Crystallization condition is a crystallization 5 hours under 120 ℃ of hydrothermal conditions.Synthetic film is as shown in table 1 to the infiltration evaporation performance of water/ethanol (10/90wt%) system.
Embodiment 7:
Changing synthetic is 28Na with the colloidal sol proportioning
2O: 1Al
2O
3: 20SiO
2: 1960H
2O, preparation process is identical with embodiment 1.Crystallization condition is a crystallization 5 hours under 120 ℃ of hydrothermal conditions.Synthetic film is as shown in table 1 to the infiltration evaporation performance of water/ethanol (10/90wt%) system.
Embodiment 8:
Tubulose α-the Al that adopts German Schumacker GmbH company to produce
2O
3As the synthetic matrix of film.Supporter applies one deck NaY type molecular sieve powder after 800 order sand paperings and ultrasonic cleaning.Synthetic identical with preparation process with embodiment 1 with the colloidal sol proportioning.Crystallization is 5 hours under 120 ℃ of hydrothermal conditions, takes out the back and washes repeatedly with deionized water.Synthetic film is applied to 75 ℃, and the infiltration evaporation performance of water/ethanol (10/90wt%) system is as shown in table 1.
Embodiment 9:
The tubulose stainless steel that supporter adopts U.S. Mott company to produce.Supporter dries after preliminary treatment such as ultrasonic cleaning, and is standby after supporter outer surface mechanical application skim NaY type molecular sieve powder.
Synthetic identical with preparation process with embodiment 1 with the colloidal sol proportioning.Crystallization is 5 hours under 120 ℃ of hydrothermal conditions.Synthetic film is applied to 75 ℃, and the infiltration evaporation performance of water/ethanol (10/90wt%) system is as shown in table 1.
Embodiment 10:
Adopt the mullite supporter, synthetic identical with preparation process with embodiment 1 with the colloidal sol proportioning.The supporter that scribbles NaY molecular sieve crystal seed is in advance vertically put into the open type glass reaction device that reaction colloidal sol is housed, and 110 ℃ of oil bath heating are reacted after 5 hours and are taken out.Wash repeatedly with deionized water.Synthetic film is applied to 75 ℃, and the infiltration evaporation performance of water/ethanol (10/90wt%) system is as shown in table 1.
Embodiment 11 (application):
Molecular screen membrane synthetic under embodiment 3 conditions is applied to the osmotic system of material liquid 1, material liquid 2 and material liquid 3, investigates the vaporization permeance property of film.Its result is as shown in table 2.
Embodiment 12 (application):
Molecular screen membrane synthetic under embodiment 9 conditions is applied to the osmotic system of material liquid 1, material liquid 2 and material liquid 3, investigates the vaporization permeance property of film.Its result is as shown in table 2.
Synthesis condition and the permeance property of table 1 embodiment 1-8
Annotate: osmotic system: 75 ℃, water/ethanol (10/90wt%); Example 10 adopts glass open formula oil bath reaction unit
The synthetic film of table 2 is applied to infiltration evaporation (vaporization infiltration) performance under the different infiltration conditions
Claims (1)
1. the preparation method of a high-performance Y type molecular sieve film is characterized in that: adopting modulus is that 3.2 waterglass is the silicon source, and aluminium hydroxide is the aluminium source, and NaOH and deionized water are synthetic liquid raw material; And employing mullite supporter; Aluminium hydroxide and NaOH are dissolved in deionized water, and adding waterglass formation mol ratio under stirring condition is 18Na
2O: 1Al
2O
3: 20SiO
2: 1260H
2The mixed liquor of O, continue to stir 2 hours colloidal sol, this colloidal sol was placed airtight polytetrafluoroethylcontainer container at room temperature still aging 12 hours, the supporter that scribbles NaY molecular sieve crystal seed is in advance vertically put into the open type glass reaction device that reaction colloidal sol is housed, 110 ℃ of oil bath heating, react after 5 hours and take out, wash repeatedly with deionized water.
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Cited By (1)
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| CN106512752A (en) * | 2016-12-05 | 2017-03-22 | 中国科学院广州能源研究所 | Method for preparing b-axial oriented ZSM-5 molecular sieve nano-ceramic composite membrane |
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| CN101648712B (en) * | 2009-09-21 | 2012-08-22 | 江西师范大学 | Method for preparing high-performance Silicalite-1 molecular sieve membrane by using TPABr as template agent |
| CN101857522B (en) * | 2010-05-24 | 2013-07-24 | 江西师范大学 | Method for separating methanol/methyl methacrylate mixed system |
| CN102451619B (en) * | 2010-10-15 | 2013-11-20 | 中国石油化工股份有限公司 | Y-shaped molecular sieve film and removal method for moisture in dichloromethane |
| CN102380320A (en) * | 2011-08-23 | 2012-03-21 | 北京中电加美环境工程技术有限责任公司 | Pervaporation hybridigation composite film as well as preparation method and application thereof |
| CN104276635B (en) * | 2014-10-29 | 2016-04-27 | 扬州大学 | The photoelectrocatalysioxidization oxidization preparation method of support type y-type zeolite membrane anode material |
| CN109607681A (en) * | 2018-11-08 | 2019-04-12 | 大连理工大学 | A kind of Y-type zeolite molecular sieve film and preparation method thereof separating underwater gold category ion |
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| CN106512752A (en) * | 2016-12-05 | 2017-03-22 | 中国科学院广州能源研究所 | Method for preparing b-axial oriented ZSM-5 molecular sieve nano-ceramic composite membrane |
| CN106512752B (en) * | 2016-12-05 | 2019-06-04 | 中国科学院广州能源研究所 | A kind of compound membrane preparation method of ZSM-5 molecular sieve nano ceramics of b- axis orientation |
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