CN105126652B - Two-stage is grafted the preparation method of zeolite filling film - Google Patents
Two-stage is grafted the preparation method of zeolite filling film Download PDFInfo
- Publication number
- CN105126652B CN105126652B CN201510502295.7A CN201510502295A CN105126652B CN 105126652 B CN105126652 B CN 105126652B CN 201510502295 A CN201510502295 A CN 201510502295A CN 105126652 B CN105126652 B CN 105126652B
- Authority
- CN
- China
- Prior art keywords
- zeolite
- grafting
- stage
- film
- preparation
- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The preparation method of two-stage grafting zeolite filling film belongs to infiltrating and vaporizing membrane separation field.Zeolite and di-isocyanate reaction are obtained into one-level modified zeolite first, cyclodextrin is subsequently adding and is carried out second graft and obtain two-stage grafting zeolite.Zeolite addition polyurethane matrix is obtained into Casting solution finally.By the solution on polyfluortetraethylene plate casting film-forming and remove solvent be obtained two-stage grafting zeolite filled polyurethane film.Process of the present invention is simple, and material is cheap and easy to get, and obtained film is compared with the filling film of unmodified zeolite with unmodified pure polyurethane film in the case where two-stage modified zeolite loading is little, and infiltration evaporation segregation index is remarkably improved.The polyurethane film of addition two-stage modified zeolite (1wt%), for the phenol/water mixture that the mass percent of phenol is 0.5%, in the case where operation temperature is 80 DEG C, PSI can reach 757.77, be 2.6 times of the polyurethane film that original zeolitic is filled under the same terms.With good prospects for commercial application.
Description
Technical field：
The present invention relates to a kind of two-stage is grafted the preparation method of zeolite filling film, belong to infiltration evaporation membrane separation technique neck
Domain.
Background technology：
Pervaporation Technology is a kind of emerging membrane separation technique process in membrance separation field, and which is considered as 21 century
One of most promising new and high technology in work field.Relative to traditional methods such as distillation, extractions, infiltration evaporation membrane separation technique has
Small investment, operating cost are low, separation efficiency is high, etc. remarkable advantage, especially it in energy consumption with traditional separation method contrast have
Sizable advantage, is particularly suitable for separating azeotropic or azeotropic mixture, or a small amount of high added value is reclaimed from big quantity of fluid
The application scenario of material, reclaims field in Organic substance in water and shows good economic advantages.The performance of infiltration evaporation
Can be by following three parameter measure, i.e. permeation flux, separation factor and infiltration evaporation segregation index.It is defined as follows：
1) permeation flux, its definition is：
In formula, M is the penetrating fluid quality for penetrating film；A is membrane area, m2；T is the operating time, h；J is permeation flux,
kg/(m2Or g/ (m h)2·h).It is such as homogeneous membrane, then is multiplied by the thickness (typically by μm in units of) of film on this basis again, then
The unit of J is kg μm/(m2Or g μm/(m h)2·h)
2) separation factor α, its definition is：
1) infiltration evaporation segregation index PSO, its definition is：
PSI=J (α -1)
In formula, A is represented；YAWith YBThe molar fraction of A and two kinds of components of B respectively in penetrant；XA
With XBThe molar fraction of A and two kinds of components of B respectively in feed liquid.
Infiltrating and vaporizing membrane is detached to it is critical only that membrane material.General single macromolecule member material is difficult to meet infiltration evaporation
Whole requirements of performance, it is therefore desirable to be modified.By taking polyurethane as an example, it is that a kind of business cheap and easy to get of low cost is high
Molecular material, with good film forming and chemical resistance.It is already used to as the infiltration vapour that Organic substance is reclaimed from water recently
Change membrane material, although single polyurethane film is fine to the affinity of Organic substance in water, the separation factor to some systems
Hundreds and thousands of (such as Das S, Banthia A K, Adhikari B.Porous polyurethane can be reached even
urea membranesfor pervaporation separation of phenol and chlorophenols from
Water [J] .Chem.Eng.J., 2008,138 (1-3)：215-223.), but generally permeation flux is very low, it is difficult to meet work
The requirement of industry, therefore be difficult to obtain more deep development in infiltration evaporation field.The separating property of PU films, people are improved further
PU membrane materials are modified using distinct methods, wherein it is filling-modified be it is most simple and easy to do, especially with through hole
The zeolite of structure, is more exposed to the attention of people.Such as Lue (Lue S J, Liaw T.Separation of xylene
mixtures using polyurethane—zeolite composite membranes[J].Desalination,
2006,193:137-143) etc. porous zeolite (Zeolite) is added in PU films and prepares organic/inorganic hybrid membrane, and
For separating xylene isomer system.As a result show, film is to the o-Dimethylbenzene (feed liquid in adjacency pair xylene different structure mixture
Middle mass content is 50%) selective, and permeability and selectivity are higher than unfilled pure PU films.
But it is found that the effective modifying function of zeolite is it has also been found that the problem that exists of some Zeolite modifyings,
There is the gap for being difficult to eliminate in such as zeolite, but this can make permeation flux greatly improve but make selectivity big with ambient polymer
It is big to decline.Therefore for the modified work of zeolite surface also begins to carry out.But as the crystalline structure of zeolite is vulnerable to the external world
The impact of the condition such as environment Acidity of Aikalinity and temperature, therefore under the premise of ensureing that zeolite pore structure is impregnable, many modified sides
Case cannot be applied to the surface of zeolite and be modified.At present to also focus on substantially simple one-level group modified for Zeolite modifying, such as
Acid treatment makes polar group in its surface band, or one-level is carried out with simplest silane coupler is modified, so selectable
Modifying agent it is extremely limited and also realize modified effect it is also unobvious.
The polyurethane film of two-stage grafting zeolite filling prepared by the present invention, is that zeolite has been carried out after one-level grafting, then
Second cyclodextrin grafting fiber is carried out on the basis of this, as the polar group number of cyclodextrin institute band is more than the original surface of zeolite
Group, so having interface compatibility preferably between polymer.This zeolite is modified to polyurethane film, will not be made
Separation factor rapid drawdown, can also improve the comprehensive separating property of film by cyclodextrin to the centrifugation of Organic substance.And entirely change
Property process it is easy, without harsh high temperature or acid-alkali treatment, remain in that the original pore passage structure of zeolite, this infiltration to keeping film
Property is beneficial.
The film that this patent is obtained shows good comprehensive separation in separating phenol/aqueous mixtures to the phenol in water
Performance.Wherein, add the polyurethane film of two-stage modified zeolite (1wt%), for the benzene that the mass percent of phenol is 0.5%
Phenol/aqueous mixtures, in the case where operation temperature is 60 DEG C, PSI can reach 472.03, be pure polyurethane film under the same terms
(209.22) 2.3 times, are 1.8 times of the polyurethane film (256.84) that original zeolitic is filled under the same terms.Therefore, it can reality
The smaller situation of loading significantly improves greatly the separating property of film, the potentiality with further development and application now.And it is right
The modified of variety classes macromolecule member material has guidance and reference.
The content of the invention：
It is an object of the invention to prepare a kind of polyurethane infiltrating and vaporizing membrane of two-stage grafting zeolite filling, which can be realized
Phenol/water mixture separates the Pervaporation Separation of phenol in phenol/aqueous mixtures.The two-stage grafting zeolite filling prepared
Polyurethane film, combine the good characteristic of inorganic, organic material, the zeolite structured loading amount in very little of two-stage grafting is
It is effectively improved the comprehensive separating property of polyurethane film.Additionally, the low raw-material cost of materials synthesis, has industrial applications
Potentiality and value.
The preparation method of the two-stage grafting zeolite filling film of the present invention is as follows：
1) first order grafting of zeolite
Zeolite and toluene diisocynate are added in the there-necked flask equipped with nitrogen protection, mechanical agitation and condensing reflux pipe
Ester, after stirring, is added dropwise to catalyst dibutyltin dilaurylate under conditions of 70 DEG C of -80 DEG C of heating in water bath, and reaction 3 is little
When obtain isocyano grafting zeolite；Subsequently using soxhlet type by the way of with N, N '-dimethyl Methanamide washing 4 times, then
With tetrahydrofuran filtering and washing 4 times, filtration product is dried 5 hours in 70 DEG C of vacuum drying ovens, is obtained surface and has been carried out the first order and connects
The zeolite of branch.
2) second level grafting of zeolite
1) first order grafting zeolite obtained in is scattered in into N under nitrogen protection, in N '-dimethyl Methanamide (DMF)
Obtain the dispersion liquid that one-level is grafted zeolite.Meanwhile, at room temperature cyclodextrin (CD) is dissolved in DMF, the solution of CD is obtained.
In there-necked flask equipped with nitrogen protection, mechanical agitation and condensing reflux pipe, one-level is grafted the solution of the dispersion liquid and CD of zeolite
Mix homogeneously, and add reaction 8 hours under catalyst dibutyltin dilaurylate, 80 degree.The mixed liquor elder generation simple filtration for obtaining, so
Washed 4 times with DMF with the method for soxhlet type afterwards, then washed 4 times with tetrahydrofuran sucking filtration, 70 degree of vacuum drying ovens are dried 5 hours, obtain
Surface has carried out the zeolite of second level grafting.
3) two-stage is grafted the preparation of zeolite filling film
2) the two-stage grafting zeolite obtained in is added into solid content for the DMF solution of the polyurethane of 10-15%, it is stirring, super
Sound dispersion, after vacuum defoamation on polyfluortetraethylene plate casting film-forming, in 80 degree solidifications 4 hours under air ambient, then by its
Heat treatment 8 hours in 150 DEG C of vacuum drying ovens are moved to, two-stage grafting zeolite filled polyurethane film is finally given.
In above procedure, 1) in the one-level grafting process of zeolite, toluene di-isocyanate(TDI) is 6 with the mass ratio of zeolite：1-
30：1, the quality consumption of dibutyl tin laurate is the 0.6% of zeolite quality；The content of isomer of toluene di-isocyanate(TDI) is
It is 60%-100% that 2,4 position isomers account for the ratio of total isomer mixture, and zeolite is in total silicon zeolite or natural zeolite
Kind.
The isomer of toluene di-isocyanate(TDI) be 2,4 position isomers and 2, position isomer, wherein 2,4 position isomers are accounted for always
The mass percent of isomer mixture is 60%-100%,
The step 2) zeolite the second level grafting in, it is characterised in that：The quality consumption of dibutyl tin laurate with
The ratio of cyclodextrin quality is 1：1750.In the DMF solution of cyclodextrin, cyclodextrin is 7 with the mass ratio of DMF：30；Cyclodextrin is
Alpha-cyclodextrin, the one kind in beta-schardinger dextrin-and gamma-cyclodextrin.
The step 3) two-stage grafting zeolite filling film preparation in, the step 3) two-stage be grafted zeolite filling film system
In standby, polyurethane is the one kind in EU and PAUR；The quality of two-stage grafting zeolite is polyurethane matter
The 1-3% of amount.
Preparation under mild conditions, can realize the two-stage grafting of zeolite surface, retain the original pore structure of zeolite, its
In, add the polyurethane film of two-stage modified zeolite (1wt%), for the phenol that the mass percent of phenol is 0.5%/water mixing
Thing, in the case where operation temperature is 60 DEG C, PSI can reach 472.03, be pure polyurethane film (209.22) under the same terms
2.3 times, be 1.8 times of polyurethane film (256.84) that original zeolitic is filled under the same terms.
Specific embodiment
Embodiment 1
1) first order grafting of zeolite
In the there-necked flask equipped with nitrogen protection, mechanical agitation and condensing reflux pipe add total silicon zeolite 5g and toluene two different
(it is the 80%) condition of 80 DEG C of heating in water bath that 2,4 position isomers account for the mass percent of total isomer mixture to cyanate 150g
Under stir after, be added dropwise to catalyst dibutyltin dilaurylate the 0.6% of zeolite quality (quality consumption for), reaction 3
Hour obtains the zeolite of isocyano grafting；Subsequently using soxhlet type by the way of with N, N '-dimethyl Methanamide washing 4 times,
Again with tetrahydrofuran filtering and washing 4 times, filtration product is dried 5 hours in 70 DEG C of vacuum drying ovens, and obtaining surface has carried out the first order
The zeolite of grafting.
2) second level grafting of zeolite
1) first order grafting zeolite obtained in is scattered in into N under nitrogen protection, in N '-dimethyl Methanamide (DMF)
Obtain the dispersion liquid that one-level is grafted zeolite.Meanwhile, 35g beta-schardinger dextrin -s (β-CD) are dissolved in in 150gDMF (ring paste at room temperature
Essence is 7 with the mass ratio of DMF：30), obtain the solution of CD.At three mouthfuls equipped with nitrogen protection, mechanical agitation and condensing reflux pipe
In bottle, one-level is grafted the solution mix homogeneously of the dispersion liquid and CD of zeolite, and plus catalyst dibutyltin dilaurylate (catalysis
Agent quality is 1 with the ratio of cyclodextrin quality：1750), 80 degree are reacted 8 hours down.The mixed liquor elder generation simple filtration for obtaining, then
Washed 4 times with DMF with the method for soxhlet type, then washed 4 times with tetrahydrofuran sucking filtration, 70 degree of vacuum drying ovens are dried 5 hours, obtain table
Face has carried out the zeolite of second level grafting.
3) two-stage is grafted the preparation of zeolite filling film
2) the two-stage grafting zeolite obtained in is added into the DMF solution of the EU that solid content is 10%, wherein
It is 1% that two-stage grafting zeolite quality is the mass percent of polyurethane, stirring, ultrasonic disperse, after vacuum defoamation in polytetrafluoroethyl-ne
Casting film-forming on alkene plate, solidifies 4 hours at 80 degree under air ambient, then heat treatment 8 is little in moving it to 150 DEG C of vacuum drying ovens
When, finally give two-stage grafting zeolite filled polyurethane film.
The film prepared using said method, tests its phenol/water penetration vaporization separating property, and charging is using phenol
Mass content is 0.5% phenol/water mixture, obtains the separating resulting such as table 1 under different temperatures：
The separating property of 1 embodiment 1 of table
Under the same terms, under 60 degree, 70 degree and 80 degree, PSI is respectively the separating property of unmodified zeolite filling film
256.84、280.72、295.27.I.e. at three temperature, zeolite is modified through two-stage, comprehensive to separate performance index PSI point
1.8 times are not improve, 2.3 times and 2.6 times.Improve effect clearly.
Embodiment 2
1) first order grafting of zeolite
Total silicon zeolite 10g and toluene two are added in the there-necked flask equipped with nitrogen protection, mechanical agitation and condensing reflux pipe
Isocyanates 60g (2,4 position isomers account for total isomer mixture mass percent be 60%, toluene di-isocyanate(TDI) with boiling
The mass ratio of stone is 6：1), after, stirring under conditions of 80 DEG C of heating in water bath, it is added dropwise to catalyst dibutyltin cinnamic acid dibutyl
Stannum (quality consumption for zeolite quality 0.6%), reaction obtains the zeolite of isocyano grafting for 3 hours；Subsequently taken out using Soxhlet
The mode N for carrying, N '-dimethyl Methanamide are washed 4 times, then with tetrahydrofuran filtering and washing 4 times, filtration product is in 70 DEG C of vacuum
Oven drying 5 hours, obtaining surface has carried out the zeolite of first order grafting.
2) second level grafting of zeolite
With 2) step in embodiment 1.
3) two-stage is grafted the preparation of zeolite filling film
2) the two-stage grafting zeolite obtained in is added into the DMF solution of the EU that solid content is 15%, wherein
It is 1% that two-stage grafting zeolite is the mass content percent of polyurethane, stirring, ultrasonic disperse, after vacuum defoamation in polytetrafluoroethyl-ne
Casting film-forming on alkene plate, solidifies 4 hours at 80 degree under air ambient, then heat treatment 8 is little in moving it to 150 DEG C of vacuum drying ovens
When, finally give two-stage grafting zeolite filled polyurethane film.
The inorganic particle filled polyurethane film prepared using said method, tests its phenol/water penetration vaporization point
From performance, charging adopts the mass content of phenol for 0.5% phenol/water mixture, obtains the separating resulting under different temperatures
Such as table 2：
The separating property of 2 embodiment 2 of table
Embodiment 3
1) first order grafting of zeolite
In the there-necked flask equipped with nitrogen protection, mechanical agitation and condensing reflux pipe add total silicon zeolite 5g and toluene two different
(it is the 100%) condition of 80 DEG C of heating in water bath that 2,4 position isomers account for the mass percent of total isomer mixture to cyanate 150g
Under stir after, be added dropwise to catalyst dibutyltin dilaurylate the 0.6% of zeolite quality (quality consumption for), reaction 3
Hour obtains the zeolite of isocyano grafting；Subsequently using soxhlet type by the way of with N, N '-dimethyl Methanamide washing 4 times,
Again with tetrahydrofuran filtering and washing 4 times, filtration product is dried 5 hours in 70 DEG C of vacuum drying ovens, and obtaining surface has carried out the first order
The zeolite of grafting.
2) second level grafting of zeolite
With 2) step in embodiment 1.
3) two-stage is grafted the preparation of zeolite filling film
2) the two-stage grafting zeolite obtained in is added into the DMF solution of the EU that solid content is 10%, wherein
It is 3% that two-stage grafting zeolite is the mass content percent of polyurethane, stirring, ultrasonic disperse, after vacuum defoamation in polytetrafluoroethyl-ne
Casting film-forming on alkene plate, solidifies 4 hours at 80 degree under air ambient, then heat treatment 8 is little in moving it to 150 DEG C of vacuum drying ovens
When, finally give two-stage grafting zeolite filled polyurethane film.
The inorganic particle filled polyurethane film prepared using said method, tests its phenol/water penetration vaporization point
From performance, charging adopts the mass content of phenol for 0.5% phenol/water mixture, obtains the separating resulting under different temperatures
Such as table 3：
The separating property of 3 embodiment 3 of table.
Claims (5)
1. two-stage is grafted the preparation method of zeolite filling film, it is characterised in that comprise the following steps：
1) first order grafting of zeolite
Addition zeolite and toluene di-isocyanate(TDI) in the there-necked flask equipped with nitrogen protection, mechanical agitation and condensing reflux pipe, 70
After stirring under conditions of DEG C -80 DEG C of heating in water bath, catalyst dibutyltin dilaurylate is added dropwise to, reaction 3 hours
To the zeolite of isocyano grafting；Subsequently using soxhlet type by the way of with N, N '-dimethyl Methanamide washing 4 times, then with four
Hydrogen furan filtering and washing 4 times, filtration product are dried 5 hours in 70 DEG C of vacuum drying ovens, and obtaining surface has carried out first order grafting
Zeolite；Toluene di-isocyanate(TDI) is 6 with the mass ratio of zeolite：1-30：1, the quality consumption of dibutyl tin laurate is zeolite
The 0.6% of quality；
2) second level grafting of zeolite
1) first order grafting zeolite obtained in is scattered in into N under nitrogen protection, in N '-dimethyl Methanamide DMF, one is obtained
The dispersion liquid of level grafting zeolite；Meanwhile, at room temperature cyclodextrin CD is dissolved in DMF, the solution of CD is obtained；Equipped with nitrogen
In the there-necked flask of protection, mechanical agitation and condensing reflux pipe, one-level is grafted the solution mix homogeneously of the dispersion liquid and CD of zeolite,
And add reaction 8 hours under catalyst dibutyltin dilaurylate, 80 degree；The mixed liquor elder generation simple filtration for obtaining, then uses Soxhlet
The method of extracting DMF is washed 4 times, then is washed 4 times with tetrahydrofuran sucking filtration, and 70 degree of vacuum drying ovens are dried 5 hours, and obtaining surface is carried out
The zeolite of second level grafting；The quality consumption of dibutyl tin laurate is 1 with the ratio of cyclodextrin quality：1750；
3) two-stage is grafted the preparation of zeolite filling film
2) the two-stage grafting zeolite obtained in is added into solid content for the DMF solution of the polyurethane of 10-15%, two-stage grafting zeolite
Quality be polyurethane quality 1-3%；Stirring, ultrasonic disperse, after vacuum defoamation on polyfluortetraethylene plate casting film-forming,
Solidify 4 hours at 80 degree under air ambient, then move it to heat treatment 8 hours in 150 DEG C of vacuum drying ovens, finally give two-stage and connect
Branch zeolite filling film.
2. preparation method according to claim 1, it is characterised in that：The step 1) in, the isomer of toluene di-isocyanate(TDI)
It is 60%-100% that content is the mass percent that 2,4 position isomers account for total isomer mixture.
3. preparation method according to claim 1, it is characterised in that：The step 1) in zeolite be total silicon zeolite or natural zeolite
In one kind.
4. preparation method according to claim 1, it is characterised in that：The step 2) in, in the DMF solution of cyclodextrin, ring paste
Essence is 7 with the mass ratio of DMF：30；Cyclodextrin is alpha-cyclodextrin, the one kind in beta-schardinger dextrin-and gamma-cyclodextrin.
5. preparation method according to claim 1, it is characterised in that：The step 3) in, polyurethane be EU and
One kind in PAUR.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510502295.7A CN105126652B (en) | 2015-08-14 | 2015-08-14 | Two-stage is grafted the preparation method of zeolite filling film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510502295.7A CN105126652B (en) | 2015-08-14 | 2015-08-14 | Two-stage is grafted the preparation method of zeolite filling film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105126652A CN105126652A (en) | 2015-12-09 |
| CN105126652B true CN105126652B (en) | 2017-03-29 |
Family
ID=54712427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510502295.7A Expired - Fee Related CN105126652B (en) | 2015-08-14 | 2015-08-14 | Two-stage is grafted the preparation method of zeolite filling film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105126652B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944578B (en) * | 2016-07-13 | 2018-05-15 | 北京工商大学 | A kind of modified seperation film and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000076634A1 (en) * | 1999-06-11 | 2000-12-21 | Gas Separation Technology, Inc. | Porous gas permeable material for gas separation |
| CN101992032A (en) * | 2010-10-26 | 2011-03-30 | 江南大学 | Polyurethane/zeolite blended oxygen-enriched membrane and preparation method thereof |
| CN102743982A (en) * | 2011-04-21 | 2012-10-24 | 北京工商大学 | Preparation method of modified polyurethane pervaporation phenol/water separation membrane |
-
2015
- 2015-08-14 CN CN201510502295.7A patent/CN105126652B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000076634A1 (en) * | 1999-06-11 | 2000-12-21 | Gas Separation Technology, Inc. | Porous gas permeable material for gas separation |
| CN101992032A (en) * | 2010-10-26 | 2011-03-30 | 江南大学 | Polyurethane/zeolite blended oxygen-enriched membrane and preparation method thereof |
| CN102743982A (en) * | 2011-04-21 | 2012-10-24 | 北京工商大学 | Preparation method of modified polyurethane pervaporation phenol/water separation membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105126652A (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Bioadhesion-inspired surface engineering constructing robust, hydrophilic membranes for highly-efficient wastewater remediation | |
| CN102327746B (en) | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof | |
| CN110026097B (en) | Preparation method of PIM-1@ MOFs/polymer composite pervaporation membrane | |
| CN102294182B (en) | Preparation method of hydrophobic nano mesoporous molecular sieve filling PDMC composite film | |
| Nigiz et al. | Pervaporation of ethanol/water mixtures using clinoptilolite and 4A filled sodium alginate membranes | |
| CN103599705B (en) | The method of organic/inorganic hybrid membrane is prepared in a kind of ultrasonic immersing | |
| CN105642133A (en) | Polyamide/COFs hybridized nanofiltration composite membrane and preparation method thereof | |
| CN104725596B (en) | A kind of Nano Silver/carbon nano-tube/poly urethane hybridized film and preparation method thereof | |
| CN103084077B (en) | Preparation method of polyurethane pervaporation phenol/water separating membrane compounded by inorganic particles | |
| CN102824856B (en) | Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology | |
| CN106492646A (en) | A kind of preparation method for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly | |
| CN101091877B (en) | Composite type membrane in use for penetrating, vaporizing and separating benzene from cyclohexane, and preparation method | |
| CN107376673B (en) | Loaded with TiO2PES ultrafiltration membrane of nanotube and preparation method and application thereof | |
| CN101003664B (en) | Latex of epoxy resin of aqueous phenolic aldehyde, and preparation method | |
| CN113713574B (en) | Preparation method of in-situ ring-opening reaction modified dual-function MOFs mixed matrix membrane | |
| CN102743982B (en) | Preparation method of modified polyurethane pervaporation phenol/water separation membrane | |
| CN104138717A (en) | Preparation method for PDMS/PAN pervaporation hollow fiber membrane | |
| CN107081068B (en) | Infiltrating and vaporizing membrane and preparation method thereof | |
| CN105126652B (en) | Two-stage is grafted the preparation method of zeolite filling film | |
| Peng et al. | Modified silica incorporating into PDMS polymeric membranes for bioethanol selection | |
| Yang et al. | Fabricating a ZIF‐8@ Polydimethylsiloxane (PDMS)/PVDF mixed matrix composite membrane for separation of ethanol from aqueous solution via vapor permeation | |
| Atazadeh et al. | Synthesis of PMHS–PDMS composite membranes embedded with silica nanoparticles and their application to separate of DMSO from aqueous solutions | |
| CN107774143A (en) | A kind of hydrotalcite tubular type hybridized film for aromatics separation/alkane and preparation method thereof | |
| CN110152503A (en) | A kind of preparation method for the solvent resistant nanofiltration membrane that graphene oxide is compound with tool microporous polymer certainly | |
| CN112156660A (en) | Metal organic framework M-gate mixed matrix membrane and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ye Hong Inventor after: Zhang Xiang Inventor after: Zhang Zhongguo Inventor after: Song Boyu Inventor after: Yu Jian Inventor after: Ma Xiaohuan Inventor after: Zuo Siyuan Inventor before: Ye Hong Inventor before: Zhang Xiang Inventor before: Zhang Guojun Inventor before: Song Boyu Inventor before: Yu Jian Inventor before: Ma Xiaohuan Inventor before: Zuo Siyuan |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170329 Termination date: 20190814 |