CN102139188B - Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane - Google Patents
Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane Download PDFInfo
- Publication number
- CN102139188B CN102139188B CN 201110000770 CN201110000770A CN102139188B CN 102139188 B CN102139188 B CN 102139188B CN 201110000770 CN201110000770 CN 201110000770 CN 201110000770 A CN201110000770 A CN 201110000770A CN 102139188 B CN102139188 B CN 102139188B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- organic
- organic composite
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention belongs to the technical field of separation membranes, and relates to a preparation method and application of a molecular sieve/organic composite infiltration, vaporization and separation membrane. The preparation method comprises the following steps of: firstly adopting a hydrothermal method to prepare nano-level molecular sieve; putting the synthesized nano-level molecular sieve in a solvent, and dispersing the molecular sieve into uniform molecular sieve suspending liquid through ultrasound, wherein the mass fraction of the molecular sieve in the suspending liquid is 5-15%; uniformly coating the molecular sieve suspending liquid on an organic supporting body; drying the organic supporting body at the temperature of 20-60 DEG C to form a molecular sieve membrane; and repeating the coating for 2-4 times. Surface modification is performed on the organic supporting body by adopting methods such as plasma induction, silane coating and the like to modify the surface hydrophily. The method can be used for preparing a large-area molecular sieve/organic composite membrane; a prepared membrane can be assembled into a spirally coiled component; and the preparation method is beneficial for industrial magnification, and has a higher industrial application value. A better separation effect can be achieved when the prepared molecular sieve/organic composite membrane is used for the infiltration and vaporization of an organic water solution system.
Description
Technical field
The invention belongs to the film separation field, be specifically related to a kind of take molecular screen material as separating layer, the organic polymer micro-filtration membrane as supporter inorganic/preparation method of organic polymer compounding permeation vaporizing film, this type of film can be used for aqueous organopolysiloxane as: the infiltration evaporation of alcohols, ethers, ketone, ester class, amine etc. separates.
Background technology
Infiltration evaporation is to utilize film to the dissolving (or absorption) of component in the liquid mixture, the difference of diffusion, realize a kind of membrane process that component is separated, the advantage such as have the efficient height, energy consumption is low, equipment is simple, the technique enlarge-effect is little, can effectively substitute the separation modes such as traditional distillation, extraction, be used for closely boiling or the removing of the separation of vapor of mixture liquid, organic solvent minor amount of water, waste water in the recovery etc. of high value organic component in a small amount of organic separation and the aqueous solution.
The principal element that affects the infiltration evaporation separating effect is physicochemical property, temperature, feed concentration, partial pressure difference of membrane material, structure and separated component etc.Wherein the selection of membrane material is crucial.Commercial hydrophilic osmotic vaporization film mainly contains two kinds at present, and a kind of is the homogeneous of the development take the hydrophily high polymer as raw material and the polymeric membrane of modification; Another kind is the inoranic membrane take the hydrophilic molecule sieve as material.Infiltration evaporation organic polymer composite membrane among the patent CN101703898A with polyvinylidene fluoride microporous filtering film (PVDF) do supporting layer, dimethyl silicone polymer is done separating layer, is applied to the separation of acetic acid aqueous solution.Patent CN1221649 is take polyacrylonitrile (PAN) as basement membrane, make PVA/PAN organic polymer composite membrane take the polyvinyl alcohol (PVA) that adds surfactant as separating layer, the adding of surfactant improves the wettability of PVA and PAN, so that separating layer and basement membrane are in conjunction with firm.It is good that macromolecule member material has pliability, filming performance is good, cost is low, be easy to the advantages such as manufacturing, but mechanical strength is not high, poor chemical stability, scarcely high temperature resistant, soda acid and organic solvent etc., be difficult under harsh conditions, use, and easily incrustation stops up, and easy cleaning not is so be restricted in the application in some field.
Zeolite membrane material be a kind of take silicon-oxy tetrahedron and aluminum-oxygen tetrahedron as basic framework, have the inorganic material in regular duct.Utilize the regular mechanism in molecular sieve crystal duct, can separate by molecule screening or selective diffusion couple organic matter.Compare with organic film, molecular sieve has good heat endurance, chemical stability, biological stability and mechanical performance.First since porous carrier has synthesized ultra-thin molecular screen membrane, the research of molecular screen membrane has obtained great progress from Suzuki in 1987 etc.The preparation of molecular screen membrane is to finish in inorganic supporting body (porous ceramics, porous metals and cellular glass) mostly at present.(the Kondo M such as Kondo, Kita H. Permeation mechanism through zeolite NaA and T-type membranes for practical dehydration of organic solvents[J]. JOURNAL OF MEMBRANE SCIENCE. 2010. 361 (1-2), 223-231) adopt hydrothermal synthesis method to synthesize NaA(A type molecular sieve take mullite porous porcelain tube as supporter) molecular screen membrane and type T molecular sieve film, and its infiltration evaporation (PV) that is used in water/second alcohol and water/methyl alcohol is permeated (VP) with steam separate.Wang(Wang X B, Zhang X F, Liu H, et al. Preparation of titanium silicalite-1 catalytic films and application as catalytic membrane reactors[J]. CHEMICAL ENGINEERING JOURNAL. 2010,156 (3), 562-570) etc. take nanoscale silicalite-I as crystal seed at porous α-Al
2O
3The success of upper employing hydrothermal synthesis method synthesized the TS-1 film, and use it in the catalytic film reactor of phenol hydroxylation.Patent CN101318665 adopts the method for high temperature enclosed hydrothermal synthesis reaction, at porous mullite pipe, tubulose α-Al
2O
3With the tubulose stainless steel be that supporting body surface has all formed the fine and close NaY type of one deck molecular screen membrane, be applied to separating of methyl alcohol/methyl tertiary butyl ether(MTBE), ethanol/ethyl tert-butyl ether (ETBE) and benzene/cyclohexane.Patent CN101284671 adopts the method for baking that crystal seed is coated on stainless steel metal wire, potsherd or the sheet glass in advance, carrier is put into synthetic liquid crystallization again, makes the L-type molecular screen membrane.
The molecular screen membrane of this preparation take inoranic membrane as supporter, its synthesis condition are comparatively harsh, and preparation cost is higher, and is difficult to avoid the inhomogeneous of thicknesses of layers, large tracts of land preparation difficulty, and it is little to load volume.Inorganic/organic composite infiltration vaporization separation film combines the selective height of organic film and the advantage that the inoranic membrane mechanical strength is high, chemical stability is good, has reduced preparation cost, has potential application prospect.
It is separating layer that the present invention adopts molecular sieve, the organic polymer micro-filtration membrane is supporter, adopt dip coating, spraying process and rolling process with nano level molecular sieve carried on organic supporter, make have good machinery with the separating property height, be applicable to molecular sieve/organic hybrid films that the aqueous organopolysiloxane infiltration evaporation separates.Method of the present invention can prepare large-area molecular sieve/organic hybrid films, and the film of making can be made into spiral wound module, solves the low problem of tubular type organic zeolite membrane filling area.
Summary of the invention
Purpose of the present invention is in order to overcome above-mentioned deficiency of the prior art, a kind of preparation method of molecular sieve/organic hybrid films is provided, can prepare large-area molecular sieve/organic hybrid films with the method, the film of making can be made into spiral wound module, solves the low problem of tubular type organic zeolite membrane filling area.
Of the present invention is the preparation method of a kind of molecular sieve/organic composite infiltration vaporization separation film, it is characterized in that may further comprise the steps:
Be dispersed into uniform molecular sieve suspension after nano-class molecular sieve placed the ultrasonic processing of solvent, and 5 ~ 20 min that vibrate under the room temperature; Wherein said suspension quality concentration is 5 ~ 15 %; Being the adhesive of 10 % with mass fraction, is (5 ~ 10) in molecular sieve suspension/binder aqueous solution mass ratio: 1 ratio, add in the molecular sieve suspension, and wherein said adhesive is polyvinyl alcohol (PVA) or silica gel; Adopt the coating embrane method evenly to be coated on organic supporter the molecular sieve suspension that has added adhesive again, 20 ~ 60 ℃ of lower oven dry, form molecular screen membrane; Repeat to film 2 ~ 4 times.
Wherein said ultrasonic processing ultrasonic power is 100 ~ 250 w among the preparation method provided by the invention.
Wherein said solvent is ethanol or water among the preparation method provided by the invention.
Coat film method described in the preparation method provided by the invention is dip coating, spraying process or rolling process.
The material of the organic supporter of conduct described in the preparation method provided by the invention is poly tetrafluoroethylene (PTFE), PVDF membrane (PVDF), acetyl cellulose film (CA), nitrocellulose filter (CN), poly (ether sulfone) film (PES) or polypropylene screen (PP) etc.; The aperture of described organic supporter is 0.005 ~ 5 μ m.
Wherein said nano-class molecular sieve is nano level NaA molecular sieve (A type molecular sieve), nanoscale Silicatile-I (the MFI molecular sieve of high silica alumina ratio) molecular sieve or nanoscale ZSM-5 molecular sieve.
Wherein take hydrophilic nano level NaA molecular sieve as suspension, when being coated on hydrophobic organic supporter, but using plasma is induced or the method such as silane-coating is carried out surface modification to hydrophobic organic supporter in the above-mentioned steps.
The preparation method of wherein said nano level NaA molecular sieve: take sodium metasilicate as the silicon source, aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=(6 ~ 9): 2: 1: (600 ~ 900) preparation Zeolite synthesis liquid; And in reactor 80 ℃ of lower crystallization 24 h, take out cooling, suction filtration is washed till neutrally and dry with deionized water, obtain nano level NaA molecular sieve.
The preparation method of wherein said nanoscale Silicatile-I molecular sieve: with NaOH, ethyl orthosilicate (TEOS), TPAOH (TPAOH) and water, by the mole proportioning
n(NaOH):
n(TEOS):
n(TPAOH):
n(H
2O)=and 1:50: 18: 1000 preparation Zeolite synthesis liquid, magnetic agitation at room temperature, aging 40 h, 100 ℃ of lower crystallization 60 h in reactor take out cooling, suction filtration, be washed till neutral and drying with deionized water, get nanoscale Silicatile-I molecular sieve;
The preparation method of wherein said nanoscale ZSM-5 molecular sieve: with NaOH, ethyl orthosilicate (TEOS), 4-propyl bromide (TPABr) and water, by the mole proportioning
n(NaOH):
n(TEOS):
n(TPABr):
n(H
2O)=and 1: 4: 1:200 preparation Zeolite synthesis liquid; Pour in the crystallizing kettle, put into 175 ℃ baking oven, crystallization 36 h take out cooling, and suction filtration is washed till neutral and drying with deionized water, gets the nanoscale ZSM-5 molecular sieve.
The application of molecular sieve/organic hybrid films of the present invention, the infiltration evaporation that can be used for aqueous organopolysiloxane separates.
The molecular sieve that the present invention synthesized/organic composite infiltration vaporization separation film can be for the membrane module of making spiral wound.
The application of the molecular sieve that the present invention synthesized/organic composite infiltration vaporization separation film is used for the separation of organic matter/aqueous systems, as: the infiltration evaporation of alcohols, ethers, ketone, ester class, amide-type and aldehydes etc. separates, and has good separating property.
The invention has the advantages that: preparation technology is simple, and the separating layer performance is controlled, and film surface continuity is good, is easy to the large tracts of land preparation.The film of preparation can be made into rolled membrane module, is convenient to increase the filling area of film, is beneficial to industry and amplifies, and has higher industrial application value.
The specific embodiment:
Embodiment 1
Take sodium metasilicate as the silicon source, aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=and 6: 2: 1: 800 preparation Zeolite synthesis liquid.Put it into the bottom with the stainless steel cauldron of polytetrafluoroethylene bushing, at 80 ℃ of lower crystallization 24 h, take out cooling, suction filtration is washed till neutral and drying with deionized water, gets nanoscale NaA molecular sieve.Water is solvent, and sonic oscillation is mixed with the suspension that mass fraction is 10 % with the NaA molecular sieve.Being the PVA aqueous solution of 10 % with mass fraction, is the ratio of 5:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.The polytetrafluoroethylene (PTFE) organic micro film that adopts dip coating to cross at plasma modification is filmed 4 times, and 60 ℃ of lower dry 24 h get NaA molecular sieve/PTFE composite membrane, and membrane area is 1.6 m
2, the separating layer thickness is about 7 μ m.Film is characterized and dimethyl formamide (DMF)/water (H
2O) the infiltration evaporation performance measurement of system.The DMF mass fraction of charging is 20 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 20 ml/min, records DMF/H
2The permeation flux of O solution infiltration evaporation is 1.24 kg m
-2H
-1, separation factor is 42, the DMF mass fraction is 0.5 % in the penetrating fluid.
Embodiment 2
Take sodium metasilicate as the silicon source, aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=and 7.5: 2: 1: 800 preparation Zeolite synthesis liquid.Put it into the bottom with the stainless steel cauldron of polytetrafluoroethylene bushing, at 80 ℃ of lower crystallization 24 h, take out cooling, suction filtration is washed till neutral and drying with deionized water, gets nanoscale NaA molecular sieve.Use water as solvent, sonic oscillation is mixed with the suspension that mass fraction is 10 % with the NaA molecular sieve.Being the PVA aqueous solution of 10 % with mass fraction, is the ratio of 10:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.The PVDF organic micro film that adopts dip coating to cross at plasma modification is filmed 3 times, and dry 24 h under the room temperature get NaA molecular sieve/PVDF composite membrane, and membrane area is 1.1m
2, the separating layer thickness is about 6 μ m.It is characterized and n-butanol/H
2The infiltration evaporation performance measurement of O system.The n-butanol mass fraction of charging is 30 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 30 ml/min, records n-butanol/H
2The permeation flux of O solution infiltration evaporation is 1.07kgm
-2H
-1, separation factor is 33, the n-butanol mass fraction of discharging is 0.5 %.
Embodiment 3
By the mole proportioning
n(NaOH):
n(TEOS):
n(TPAOH):
n(H
2O)=and 0.5:25: 9: 500 preparation Zeolite synthesis liquid, magnetic agitation at room temperature, aging 40 h, put it into the bottom with the stainless steel cauldron of polytetrafluoroethylene bushing, at 100 ℃ of lower crystallization 60 h, take out cooling, suction filtration, be washed till neutral and drying with deionized water, get nanoscale Silicatile-I molecular sieve.Make solvent with ethanol, sonic oscillation is mixed with the suspension that mass fraction is 10 % with the Silicatile-I molecular sieve.Being the PVA aqueous solution of 10 % with mass fraction, is the ratio of 8:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.Adopt dip coating to film 3 times at the PP organic micro film, dry 24 h under the room temperature get Silicatile-I molecular sieve/PP composite membrane, and membrane area is 0.4 m
2, the separating layer thickness is about 6 μ m.It is characterized and acetone/H
2The infiltration evaporation performance measurement of O system.The acetone quality mark of charging is 30 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 35 ml/min, records acetone/H
2The permeation flux of O solution infiltration evaporation is 0.89kg m
-2H
-1, separation factor is 26, the acetone quality mark of discharging is 0.3 %.
Embodiment 4
By the mole proportioning
n(NaOH):
n(TEOS):
n(TPABr):
n(H
2O)=and 1: 4: 1:200 preparation Zeolite synthesis liquid.Pour in the band teflon-lined stainless steel crystallizing kettle, put into 175 ℃ baking oven, crystallization 36 h take out cooling, and suction filtration is washed till neutrality and dry with deionized water, gets the nanoscale ZSM-5 molecular sieve.Use water as solvent, sonic oscillation is mixed with the suspension that mass fraction is 10 % with ZSM-5 molecular sieve.Being the PVA aqueous solution of 10 % with mass fraction, is the ratio of 5:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.Adopt dip coating to film 3 times at the PP organic micro film, dry 24 h under the room temperature get ZSM-5 molecular sieve/PP composite membrane, and membrane area is 0.4 m
2, the separating layer thickness is about 7 μ m.It is characterized and isopropyl alcohol/H
2The infiltration evaporation performance measurement of O system.The isopropyl alcohol mass fraction of charging is 25 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 30 ml/min, records isopropyl alcohol/H
2The permeation flux of O solution infiltration evaporation is 1.00kg m
-2H
-1, separation factor is 19, the isopropyl alcohol mass fraction of discharging is 0.4 %.
Claims (1)
1. the preparation method of molecular sieve/organic composite infiltration vaporization separation film is characterized in that may further comprise the steps: after being placed the ultrasonic processing of solvent, nano-class molecular sieve is dispersed into uniform molecular sieve suspension, and 5 ~ 20 min that vibrate under the room temperature; Wherein said suspension quality concentration is 5 ~ 15 %; Being the adhesive of 10 % with mass fraction, is (5 ~ 10) in molecular sieve suspension/binder aqueous solution mass ratio: 1 ratio, add in the molecular sieve suspension, and wherein said adhesive is polyvinyl alcohol (PVA) or silica gel; Adopt the coating embrane method evenly to be coated on organic supporter the molecular sieve suspension that has added adhesive again, 20 ~ 60 ℃ of lower oven dry, form molecular screen membrane; Repeat to film 2 ~ 4 times;
Wherein said ultrasonic processing ultrasonic power is 100 ~ 250 w; Wherein said solvent is ethanol or water, and wherein said coat film method is dip coating, spraying process or rolling process.
2, the preparation method of described molecular sieve/organic composite infiltration vaporization separation film according to claim 1 is characterized in that wherein said material as organic supporter is poly tetrafluoroethylene (PTFE), PVDF membrane (PVDF), acetyl cellulose film (CA), nitrocellulose filter (CN), poly (ether sulfone) film (PES) or polypropylene screen (PP); The aperture of described organic supporter is 0.005 ~ 5 μ m.
3, the preparation method of described molecular sieve/organic composite infiltration vaporization separation film according to claim 1, it is characterized in that wherein take hydrophilic nano level NaA molecular sieve as suspension, when being coated on hydrophobic organic supporter, using plasma is induced or the silane-coating method is carried out surface modification to hydrophobic organic supporter.
4, the preparation method of described molecular sieve/organic composite infiltration vaporization separation film according to claim 1 is characterized in that wherein said nano-class molecular sieve is nano level NaA molecular sieve, nanoscale Silicatile-I molecular sieve or nanoscale ZSM-5 molecular sieve.
5, the preparation method of described molecular sieve/organic composite infiltration vaporization separation film according to claim 4, it is characterized in that the preparation method of wherein said nano level NaA molecular sieve: take sodium metasilicate as the silicon source, aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=(6 ~ 9): 2: 1: (600 ~ 900) preparation Zeolite synthesis liquid; And in reactor 80 ℃ of lower crystallization 24 h, take out cooling, suction filtration is washed till neutrally and dry with deionized water, obtain nano level NaA molecular sieve.
6, the preparation method of described molecular sieve/organic composite infiltration vaporization separation film according to claim 4, the preparation method who it is characterized in that wherein said nanoscale Silicatile-I molecular sieve: with NaOH, ethyl orthosilicate (TEOS), TPAOH (TPAOH) and water, by the mole proportioning
n(NaOH):
n(TEOS):
n(TPAOH):
n(H
2O)=and 1:50: 18: 1000 preparation Zeolite synthesis liquid, magnetic agitation at room temperature, aging 40 h, 100 ℃ of lower crystallization 60 h in reactor take out cooling, suction filtration, be washed till neutral and drying with deionized water, get nanoscale Silicatile-I molecular sieve.
The application of the molecular sieve that 7, the preparation method of any one molecular sieve/organic composite infiltration vaporization separation film makes among the claim 1-6/organic composite infiltration vaporization separation film can be used for the infiltration evaporation separation of aqueous organopolysiloxane or the separation of organic matter/aqueous systems.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110000770 CN102139188B (en) | 2011-01-05 | 2011-01-05 | Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110000770 CN102139188B (en) | 2011-01-05 | 2011-01-05 | Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102139188A CN102139188A (en) | 2011-08-03 |
| CN102139188B true CN102139188B (en) | 2013-10-30 |
Family
ID=44407121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110000770 Expired - Fee Related CN102139188B (en) | 2011-01-05 | 2011-01-05 | Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102139188B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CA2849643A1 (en) * | 2011-09-22 | 2013-03-28 | Ngk Insulators, Ltd. | Method for producing carbon membrane |
| CN102500243A (en) * | 2011-11-17 | 2012-06-20 | 常州大学 | Preparation method for molecular sieve/organic composite permeable vaporization membrane |
| JP6107809B2 (en) * | 2012-02-24 | 2017-04-05 | 三菱化学株式会社 | Porous support-zeolite membrane composite |
| CN102583430A (en) * | 2012-03-01 | 2012-07-18 | 浙江大学 | Method for synthesizing NaA-type molecular sieve membrane on inner wall of support body |
| EP2719445A1 (en) * | 2012-10-09 | 2014-04-16 | Clariant International Ltd. | Process for concentrating small organic molecules from liquid or gaseous mixtures using a composite membrane comprising a fluoropolymer and hydrophobic siliceous particles |
| CN103846011B (en) * | 2012-12-05 | 2015-09-09 | 天津工业大学 | A kind of conducting polymer perforated membrane |
| CN102974227B (en) * | 2012-12-05 | 2015-03-11 | 天津工业大学 | Method for preparing polymer conductive porous membrane |
| CN103861464B (en) * | 2012-12-10 | 2017-09-26 | 天津工业大学 | A kind of preparation method of molecular sieve micro mist modification polyvinylidene fluoride film |
| CN104841289B (en) * | 2015-04-17 | 2017-06-27 | 大连理工大学 | It is a kind of to synthesize NaA type molecular screen membranes and preparation method thereof on organic hollow fiber surface |
| CN106000124B (en) * | 2016-06-26 | 2018-07-17 | 北京工业大学 | A kind of acid proof surface modifying method of raising NaA molecular sieve membrane and application |
| CN107051579A (en) * | 2017-06-06 | 2017-08-18 | 江西师范大学 | A kind of method that use Ti MWW molecular screen membranes prepare benzenediol |
| CN107081078B (en) * | 2017-06-16 | 2019-12-06 | 常州大学 | preparation method of nano-structure composite ultrafiltration membrane |
| CN107626213B (en) * | 2017-11-13 | 2020-12-11 | 浙江富铭工业机械有限公司 | Preparation method of hydrophilic molecular sieve membrane |
| CN108250040A (en) * | 2018-01-11 | 2018-07-06 | 福建华夏蓝新材料科技有限公司 | A kind of method that alcohol solution separates and recovers in high purity aluminium oxide production |
| CN108795929A (en) * | 2018-07-06 | 2018-11-13 | 大连元和健路医学检验实验室有限公司 | A kind of preparation method of DNA molecular sieve pillar |
| CN108854571B (en) * | 2018-07-11 | 2020-10-30 | 常州大学 | Method for preparing separation membrane by ultrasonic atomization deposition method |
| CN113543869A (en) * | 2019-01-09 | 2021-10-22 | 沙特基础工业全球技术公司 | Dehydration of glycol-containing mixtures with high water content using optimized pervaporation |
| CN110112447B (en) * | 2019-05-09 | 2022-08-02 | 朝阳华鼎储能技术有限公司 | Multi-layer composite proton exchange membrane containing perfluorinated sulfonic acid resin and preparation method thereof |
| CN110624522A (en) * | 2019-09-26 | 2019-12-31 | 中国原子能科学研究院 | Preparation method of silicon-based molecular sieve membrane material for adsorbing uranium hexafluoride |
| CN111439472A (en) * | 2020-03-26 | 2020-07-24 | 河北迪纳兴科生物科技有限公司 | Molecular sieve package and preparation method and application thereof |
| CN111408287A (en) * | 2020-04-24 | 2020-07-14 | 常州大学 | Method for preparing defect-free microporous organic silicon film on hydrophobic mesoporous organic silicon surface by spin coating method |
| CN111992051B (en) * | 2020-09-10 | 2023-09-29 | 南京惟新环保装备技术研究院有限公司 | ZSM-5 type molecular sieve membrane capable of improving orientation and preparation method thereof |
| CN113634138B (en) * | 2021-08-23 | 2023-01-24 | 华东理工大学 | Dynamic hydrothermal synthesis hollow fiber outer wall SUZ-4 type molecular sieve pervaporation membrane and method for removing methanol by using solvent thereof |
| CN115286495A (en) * | 2022-08-23 | 2022-11-04 | 江西师范大学 | Method for preparing acrolein by catalytic oxidation of glycerol through ZSM-5 molecular sieve membrane |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002058972A (en) * | 2000-08-17 | 2002-02-26 | National Institute Of Advanced Industrial & Technology | Composite membrane of porous organic high polymer membrane and zeolite, and method of manufacturing for the same |
| JP2008043864A (en) * | 2006-08-14 | 2008-02-28 | Asahi Kasei Chemicals Corp | Zeolite composite membrane and its manufacturing method |
| CN100547131C (en) * | 2007-11-28 | 2009-10-07 | 吉林大学 | The preparation of coaxial spinning technology has the method for hierarchical organization hollow molecules sieve fiber |
| CN101544379B (en) * | 2009-04-30 | 2012-06-06 | 浙江大学 | Method for synthesizing molecular sieve membrane by dip coating-rubbing crystal-coating method |
| 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 |
-
2011
- 2011-01-05 CN CN 201110000770 patent/CN102139188B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102139188A (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102139188B (en) | Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane | |
| Wenten et al. | LTA zeolite membranes: current progress and challenges in pervaporation | |
| Zeng et al. | Superhydrophilic and underwater superoleophobic MFI zeolite-coated film for oil/water separation | |
| Sebastian et al. | Microwave-assisted hydrothermal rapid synthesis of capillary MFI-type zeolite–ceramic membranes for pervaporation application | |
| Zhang et al. | Mass transfer model, preparation and applications of zeolite membranes for pervaporation dehydration: A review | |
| US6387269B1 (en) | Membrane for separating fluids | |
| Liu et al. | Hydrophilicity-controlled MFI-type zeolite-coated mesh for oil/water separation | |
| US9375678B2 (en) | Metal-organic framework supported on porous polymer | |
| Peng et al. | Preparation of zeolite MFI membranes on defective macroporous alumina supports by a novel wetting–rubbing seeding method: Role of wetting agent | |
| CN102350229B (en) | Metal element modified ZSM-5 molecular sieve composite membrane as well as preparation method and application thereof | |
| JP3670852B2 (en) | Production method of mixture separation membrane | |
| US8721891B2 (en) | Zeolite membrane, separation membrane, and component separation method | |
| JP6158437B2 (en) | High-strength hollow fiber type molecular sieve membrane and method for producing the same | |
| CN101318665B (en) | Method for preparing high-performance Y type molecular sieve film and application of the same in organic mixture separation | |
| CN101716470B (en) | Method for preparing fluorine-containing mordenite zeolite membrane | |
| Yuan et al. | Synthesis and characterization of high performance NaA zeolite-polyimide composite membranes on a ceramic hollow fiber by dip-coating deposition | |
| Zhang et al. | Preparation of high-flux zeolite T membranes using reusable macroporous stainless steel supports in fluoride media | |
| Jiang et al. | Effect of Si/Al ratio in the framework on the pervaporation properties of hollow fiber CHA zeolite membranes | |
| Xu et al. | Silver-exchanged zeolite LTA molecular sieving membranes with enhanced hydrogen selectivity | |
| CN102500243A (en) | Preparation method for molecular sieve/organic composite permeable vaporization membrane | |
| Yu et al. | In situ impregnation− gelation− hydrothermal crystallization synthesis of hollow fiber zeolite NaA membrane | |
| Wu et al. | Separation of ethyl acetate (EA)/water by tubular silylated MCM-48 membranes grafted with different alkyl chains | |
| CN101259383B (en) | Acidproof zeolite molecular sieve membrane for separating liquid mixture and preparation thereof | |
| Wu et al. | Preparation of chabazite zeolite membranes by a two-stage varying-temperature hydrothermal synthesis for water-ethanol separation | |
| US8263179B2 (en) | Process for producing zeolite separation membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131030 Termination date: 20220105 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |