CN106975372B - Mixed substrate membrane containing nano-grade molecular sieve and preparation method and application based on flaky material filling - Google Patents
Mixed substrate membrane containing nano-grade molecular sieve and preparation method and application based on flaky material filling Download PDFInfo
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- CN106975372B CN106975372B CN201710252642.4A CN201710252642A CN106975372B CN 106975372 B CN106975372 B CN 106975372B CN 201710252642 A CN201710252642 A CN 201710252642A CN 106975372 B CN106975372 B CN 106975372B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The present invention discloses a kind of mixed substrate membrane containing nano-grade molecular sieve based on flaky material filling, and the mixed substrate membrane containing nano-grade molecular sieve is dispersed in the intracorporal nano silver slice of polyether-polyamide block copolymer and is formed by polyether-polyamide block copolymer and filling.The mixed substrate membrane containing nano-grade molecular sieve is to CO2/CH4Gaseous mixture and CO2/N2The Selective Separation CO of gaseous mixture2Test result shows, its permselective property data has been more than the 2008Robeson upper limit, illustrate the carbon dioxide separation performance that effective carbon-dioxide transmission channels reinforced film is constructed using nano silver slice smooth surface, overcome " trade-off " effect, the gas permeability and selectivity for improving film are the effective methods for improving mixed-matrix film properties.
Description
Technical field
The invention belongs to field of membrane material, and in particular to a kind of mixed substrate membrane containing nano-grade molecular sieve based on flaky material filling, especially
For carbon dioxide gas separation membrane material, and its preparation method and application.
Background technique
Natural gas and biogas are important industrial chemicals and clean energy resource, usually contain in freshly harvested natural gas and biogas
The sour gas such as carbon dioxide, these sour gas not only influence gaseous mass, but also meeting heavy corrosion pipeline and equipment, institute
These sour gas must be being removed before, and carbon capture becomes a necessary and crucial industrial process.It is efficiently low
Energy consumption and environmental-friendly collecting carbonic anhydride technology are the key that solve energy gas purifying problem.Membrane technology with its efficiently,
The features such as green, low-carbon, shows good development prospect in collecting carbonic anhydride field, develops high osmosis, highly selective two
Carbonoxide separation membrane material has important theoretical value and realistic meaning.
Gas separation membrane material refers to that the material for having selective penetrated property to substance, organic high molecular layer are separated as gas
Membrane material has the following characteristics that with good film forming, thermal stability, mechanical performance and solvent resistant and other chemical substances.
However, nearly all high molecular material that is ready-made, can forming a film has a common problem: all gas permeability coefficients
Big film, separation selection coefficient are lower；The high film of all separation selection coefficients, gas permeability coefficient is lower, i.e. " trade-
Off " effect.Mixed substrate membrane containing nano-grade molecular sieve can overcome a kind of membrane material of " trade-off " effect to have become this field as one kind
Research hotspot.Currently used for prepare particle filled composite used in composite membrane for example zeolite, carbon molecular sieve, nanotube, metal organic frame,
Graphene etc..
In recent years, the continuous development studied in terms of mixed substrate membrane containing nano-grade molecular sieve with researcher, constructs carbon dioxide in film
Transmission channels thought is as a kind of concern for efficiently separating method and having caused researchers.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the existing defects, provides a kind of for carbon dioxide gas separation
Based on flaky material filling mixed substrate membrane containing nano-grade molecular sieve.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
Based on flaky material filling mixed substrate membrane containing nano-grade molecular sieve, the mixed substrate membrane containing nano-grade molecular sieve by polyether-polyamide block copolymer with
And filling is dispersed in the intracorporal nano silver slice composition of polyether-polyamide block copolymer.
Preferably, the mass ratio of the polyether-polyamide block copolymer and nano silver slice is 1:0.02~1:0.08.
It is highly preferred that the mass ratio of the polyether-polyamide block copolymer and nano silver slice is 1:0.04~1:0.06.
Preferably, the mixed substrate membrane containing nano-grade molecular sieve with a thickness of 50~80 μm.
The preparation method of above-mentioned mixed substrate membrane containing nano-grade molecular sieve, comprising: polyether-polyamide block copolymer is first dissolved in alcohol-water
In the mixed solvent adds nano silver slice, after mixing, is cast, is dried to obtain the mixed substrate membrane containing nano-grade molecular sieve.
Preferably, the nano silver slice passes through the method included the following steps and is made: first by silver nitrate and polyvinyl pyrrole
Alkanone is added to the water, and after dissolution, sequentially adds sodium citrate, sodium borohydride, hydrogen peroxide and hydrazine hydrate, after the reaction was completed, point
From obtaining nano silver slice.After sodium citrate is added, becomes light grey to solution, sodium borohydride is added, after adding sodium borohydride
Hydrogen peroxide is added immediately, is stirred to react (about 30min), then hydrazine hydrate is added dropwise, continues to be stirred to react (about 1h), shading is stood.Its
In, polyvinylpyrrolidone promotes to form uniform nanometer sheet as dispersing agent；Sodium citrate controls { 100 } as stabilizer
The speed of growth in face promotes to generate nanometer sheet；Sodium borohydride, which rises, is used as reducing agent, restores silver ion；Hydrogen peroxide as oxidant,
The reduction of silver is reduced, irregular small silver particles are etched；Hydrazine hydrate makes the silver-colored simple substance newly restored along laterally flat as reducing agent
It looks unfamiliar length.
Preferably, the mass ratio of the silver nitrate, polyvinylpyrrolidone and sodium citrate be 1:0.5:(0.1~
0.09)；The silver nitrate, sodium borohydride, hydrogen peroxide and hydrazine hydrate molar ratio be 1:0.001:(4.5~5): (4~4.5),
Preferably, the molar ratio of the silver nitrate, sodium borohydride, hydrogen peroxide and hydrazine hydrate is 1:0.001:4.9:4.
Above-mentioned mixed substrate membrane containing nano-grade molecular sieve can be used for Selective Separation CO2Gas.As UF membrane removes the CO in natural gas or biogas2
Gas.
Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve is to CO2/CH4Gaseous mixture and CO2/N2The Selective Separation CO of gaseous mixture2Examination
Test the result shows that, permselective property data have been more than the 2008Robeson upper limit, illustrate to construct using nano silver slice smooth surface
The carbon dioxide separation performance of effective carbon-dioxide transmission channels reinforced film overcomes " trade-off " effect, improves the gas of film
Permeability and selectivity are the effective methods for improving mixed-matrix film properties.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the scanning electron microscope (SEM) photograph of nano silver slice obtained by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section obtained by embodiment 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section obtained by embodiment 2；
Fig. 4 is the scanning electron microscope (SEM) photograph of Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section obtained by embodiment 3；
Fig. 5 is the scanning electron microscope (SEM) photograph of Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section obtained by embodiment 4；
Fig. 6 is the scanning electron microscope (SEM) photograph of pure Pebax film section obtained by comparative example.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
Prepare Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve, the mixed substrate membrane containing nano-grade molecular sieve with a thickness of 55 μm, the mixed substrate membrane containing nano-grade molecular sieve with
Polyether-polyamide block copolymer (1657, it is abbreviated as Pebax) it is membrane matrix, nano silver slice is added in membrane matrix,
Wherein, the mass ratio 1:0.02 of Pebax and nano silver slice, the preparation process of the mixed substrate membrane containing nano-grade molecular sieve are as follows:
Step 1, nano silver slice are prepared using solution phase chemical reduction:
Take silver nitrate (AgNO3, 3.4g) and polyvinylpyrrolidone (PVP, 1.7g) be dissolved in deionized water (100mL),
Then solution is poured into mechanical stirring in three-necked flask (600r/min) by ultrasonic disperse, 4mL sodium citrate is added into solution
(0.3mol/L) becomes light grey to solution, 1mL sodium borohydride (0.02mol/L) solution is added into solution, and be added immediately
10mL hydrogen peroxide (30%) continues to stir 30min.5mL hydrazine hydrate (80%) is dissolved in 50mL deionized water, is dripped by constant pressure
Liquid funnel is slowly added into reaction solution, after dripping off, adjusts revolving speed 800r/min, continues to stir 1h.Reaction solution is poured into completely
Beaker in, shading is sealed at 25 DEG C and places 48h, centrifugation (8000r/min) washing, obtained after dry gray precipitate to get
Nano silver slice.Fig. 1 is the scanning electron microscope (SEM) photograph of nano silver slice obtained by embodiment 1.
Step 2 weighs 2.5g Pebax grain dissolution in the ethanol water that concentration is 70wt%, stirs at 80 DEG C
8h, so that Pebax particle all dissolves, it is 4%Pebax solution that mass fraction, which is prepared, spare.
Nano silver slice made from step 1 (0.05g) is added in Pebax solution made from step 2 by step 3, in room temperature
Lower stirring 8h, obtains casting solution.Resulting casting solution is poured on clean ultra-flat surface ware and is cast, the dry 48h at 25 DEG C,
Then it puts it into 50 DEG C of vacuum drying ovens and removes remaining solvent, obtain Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve, obtain thickness
The mixed substrate membrane containing nano-grade molecular sieve that degree is 55 μm.Fig. 2 is the scanning electron microscope (SEM) photograph of obtained Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section.
Under the conditions of 25 DEG C, 2bar, it is used for Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve to separate CO2Volume fraction is 10%
CO2/CH4Gaseous mixture, CO2Flux is 340barrer, CO2/CH4Selectivity is 31；The mixed substrate membrane containing nano-grade molecular sieve is used for CO2Body
The CO that fraction is 10%2/N2Gaseous mixture, CO2Flux is 316barrer, CO2/N2Selectivity 55.
Embodiment 2
Unlike the first embodiment: mixed substrate membrane containing nano-grade molecular sieve with a thickness of 64 μm, wherein the mass ratio of Pebax and nano silver slice
1:0.04.Fig. 3 is the scanning electron microscope (SEM) photograph of obtained Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section.
Under the conditions of 25 DEG C, 2bar, it is used for obtained Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve to separate CO2Volume point
The CO that number is 10%2/CH4Gaseous mixture, CO2Flux is 443barrer, CO2/CH4Selectivity is 40；The mixed substrate membrane containing nano-grade molecular sieve is used
In separation CO2The CO that volume fraction is 10%2/N2Gaseous mixture, CO2Flux is 404barrer, CO2/N2Selectivity 58.
Embodiment 3
With embodiment 1 except that: film with a thickness of 76 μm, wherein the mass ratio 1 of Pebax and nano silver slice:
0.06.Fig. 4 is the scanning electron microscope (SEM) photograph of obtained Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section.
Under the conditions of 25 DEG C, 2bar, it is used for obtained Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve to separate CO2Volume point
The CO that number is 10%2/CH4Gaseous mixture, CO2Flux is 349barrer, CO2/CH4Selectivity is 44；The mixed substrate membrane containing nano-grade molecular sieve is used
In separation CO2The CO that volume fraction is 10%2/N2Gaseous mixture, CO2Flux is 365barrer, CO2/N2Selectivity 56.
Embodiment 4
With embodiment 1 except that: film with a thickness of 79 μm, wherein the mass ratio 1 of Pebax and nano silver slice:
0.08.Fig. 5 is the scanning electron microscope (SEM) photograph of obtained Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve section.
Under the conditions of 25 DEG C, 2bar, it is used for obtained Pebax- nano silver slice mixed substrate membrane containing nano-grade molecular sieve to separate CO2Volume point
The CO that number is 10%2/CH4Gaseous mixture, CO2Flux is 221barrer, CO2/CH4Selectivity is 31.7；By the mixed substrate membrane containing nano-grade molecular sieve
For separating CO2The CO that volume fraction is 10%2/N2Gaseous mixture, CO2Flux is 226barrer, CO2/N2Selectivity 41.5.
Comparative example 1
2.5g Pebax grain dissolution is weighed in the ethanol water that concentration is 70wt%, after 80 DEG C of stirring 8h, is obtained
To casting solution.Resulting casting solution is poured on clean ultra-flat surface ware and is cast, is dried at room temperature for 48h, then put
Enter in 50 DEG C of vacuum drying ovens for 24 hours to remove remaining solvent, obtains the Pebax film with a thickness of 60 μm.Fig. 6 is obtained pure
The scanning electron microscope (SEM) photograph of Pebax film section.
Under the conditions of 25 DEG C, 2bar, it is used for obtained pure Pebax film to separate CO2The CO that volume fraction is 10%2/
CH4Gaseous mixture, CO2Flux is 281barrer, CO2/CH4Selectivity is 30；For separating CO2Volume fraction is 10%
CO2/N2Gaseous mixture, CO2Flux is 305barrer, CO2/N2Selectivity 54.
Comparative example 2
Prepare Pebax- nano-Ag particles mixed substrate membrane containing nano-grade molecular sieve, the mixed substrate membrane containing nano-grade molecular sieve with a thickness of 76 μm, the mixed substrate membrane containing nano-grade molecular sieve
Using Pebax as membrane matrix, nano-Ag particles are added in membrane matrix, wherein the mass ratio 1 of Pebax and nano-Ag particles:
0.06, the preparation process of the mixed substrate membrane containing nano-grade molecular sieve is as follows:
Step 1, nano-Ag particles are prepared using hydro-thermal method:
It takes cetyl trimethylammonium bromide (CTAB, 1.0g) to be dissolved in deionized water (20mL), after stirring and dissolving, is added
The glucose solution 10mL of 0.25mol/L, futher stirs dissolution, and the solution dissolved is poured into reaction kettle and is built in 150 DEG C
Muffle reaction in furnace 8h, after the reaction was completed, by solution centrifuge washing it is dry after, obtain nano-Ag particles product.
Step 2 weighs 2.5g Pebax grain dissolution in the ethanol water that concentration is 70wt%, stirs at 80 DEG C
8h, so that Pebax particle all dissolves, it is 4%Pebax solution that mass fraction, which is prepared, spare.
Nano-Ag particles made from step 1 (0.15g) are added in Pebax solution made from step 2 by step 3, in room
Temperature is lower to stir 8h, obtains casting solution.Resulting casting solution is poured on clean ultra-flat surface ware and is cast, it is dry at 25 DEG C
Then 48h puts it into 50 DEG C of vacuum drying ovens and removes remaining solvent, obtain Pebax- nano-Ag particles mixed substrate membrane containing nano-grade molecular sieve,
Obtain the mixed substrate membrane containing nano-grade molecular sieve with a thickness of 76 μm.
Under the conditions of 25 DEG C, 2bar, it is used for Pebax- nano-Ag particles mixed substrate membrane containing nano-grade molecular sieve to separate CO2Volume fraction is
10% CO2/CH4Gaseous mixture, CO2Flux is 304barrer, CO2/CH4Selectivity is 30；The mixed substrate membrane containing nano-grade molecular sieve is used for
CO2The CO that volume fraction is 10%2/N2Gaseous mixture, CO2Flux is 319barrer, CO2/N2Selectivity 54.
Table 1 is Pebax- nano silver mixed substrate membrane containing nano-grade molecular sieve Selective Separation CO2Result
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (8)
1. based on the mixed substrate membrane containing nano-grade molecular sieve of flaky material filling, the mixed substrate membrane containing nano-grade molecular sieve by polyether-polyamide block copolymer and
Filling is dispersed in polyether-polyamide block copolymer intracorporal nano silver slice composition, the polyether-polyamide block copolymer with
The mass ratio of nano silver slice is 1:0.02~1:0.06.
2. mixed substrate membrane containing nano-grade molecular sieve according to claim 1, it is characterised in that: the polyether-polyamide block copolymer with receive
The mass ratio of rice silver strip is 1:0.04~1:0.06.
3. mixed substrate membrane containing nano-grade molecular sieve according to claim 1, it is characterised in that: the mixed substrate membrane containing nano-grade molecular sieve with a thickness of 50~80 μ
m。
4. the preparation method of any mixed substrate membrane containing nano-grade molecular sieve of claim 1-3, comprising: first by polyether-polyamide block copolymer
It is dissolved in ethanol-water mixed solvent, adds nano silver slice, after mixing, be cast, be dried to obtain the mixed substrate membrane containing nano-grade molecular sieve.
5. the preparation method according to claim 4, it is characterised in that: the nano silver slice passes through the side included the following steps
Method be made: first silver nitrate and polyvinylpyrrolidone are added to the water, after dissolution, sequentially add sodium citrate, sodium borohydride,
Hydrogen peroxide and hydrazine hydrate, after the reaction was completed, isolated nano silver slice.
6. preparation method according to claim 5, it is characterised in that: the silver nitrate, polyvinylpyrrolidone and lemon
The mass ratio of sour sodium is 1:0.5:(0.1~0.09), the silver nitrate, sodium borohydride, hydrogen peroxide and hydrazine hydrate molar ratio be
1:0.001:(4.5~5): (4~4.5).
7. the application of mixed substrate membrane containing nano-grade molecular sieve described in claim 1, it is characterised in that: the mixed substrate membrane containing nano-grade molecular sieve is used for Selective Separation CO2
Gas.
8. application according to claim 7, it is characterised in that: the mixed substrate membrane containing nano-grade molecular sieve for UF membrane remove natural gas or
CO in biogas2Gas.
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| CN109865439A (en) * | 2019-01-22 | 2019-06-11 | 石河子大学 | A kind of mixed substrate membrane containing nano-grade molecular sieve and preparation method and application of the filling of ZIF-8/ graphite phase carbon nitride |
| CN110227361B (en) * | 2019-05-31 | 2021-09-03 | 太原理工大学 | Preparation method and application of metakaolin and carbon nanotube synergistically modified mixed matrix membrane |
| CN111013409B (en) * | 2019-12-27 | 2021-12-21 | 天津工业大学 | Mixed matrix membrane filled with lanthanide fluoride porous nanosheets and preparation method and application thereof |
| CN112675720B (en) * | 2020-12-10 | 2023-03-24 | 石河子大学 | Preparation method and application of mixed matrix membrane filled with bimetallic strip material |
| CN115990415A (en) * | 2022-10-27 | 2023-04-21 | 塔里木大学 | Mixed matrix film based on ultrathin vermiculite nano sheet filling, and preparation method and application thereof |
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| CN105854651A (en) * | 2016-04-06 | 2016-08-17 | 中国石油大学(华东) | High-permeability mixed matrix membrane as well as preparation method and application thereof |
| CN106268380A (en) * | 2016-09-19 | 2017-01-04 | 石河子大学 | A kind of polyelectrolyte film based on Glycine sodium and its preparation method and application |
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