CN101069820A - Method for preparing chitosan and surface modified Y-type zeolite hybridization liquid separation film - Google Patents
Method for preparing chitosan and surface modified Y-type zeolite hybridization liquid separation film Download PDFInfo
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Abstract
The present invention discloses a preparation method of chitosan and surface-modified Y-type zeolite hybrid liquid separation membrane, belonging to the field of organic-inorganic hybrid liquid separation membrane preparation technology. Said method includes the following steps: converting NaY type zeolite into hydrogen type zeolite; respectively adopting 3-aminopropyltriethoxysilane and 3-mercaptopropyltriethoxysilane to make surface modification of hydrogen type zeolite so as to obtain Y-type zeolite with amino-group and Y-type zeolite with mercapto-group, oxidating mercapto-group to obtain Y-type zeolite with sulfoacid racical; making the above-mentioned modified zeolite be dispersed in acetic acid aqueous solution, then adding chitosan, stirring them and dissolving them, utiling stirring and ultrasonic dispersion to obtain membrane-casting liquor, filtering, standing still, defoaming, casting to form membrane on the plate glass, using sulfuric acid solution to make membrane cross-linking reaction, using deionized water to clean it, vacuum-drying so as to obtain the chitosan-surface modified Y-type zeolite hybrid membrane.
Description
Technical field
The present invention relates to the preparation method of a kind of shitosan and surface modified Y-type zeolite hybridization liquid separation film.Belong to hybrid inorganic-organic fluid separation applications membrane preparation technology.
Background technology
Fuel cell is a kind ofly directly the chemical energy in fuel and the oxidant to be converted into the efficient generating apparatus of electric energy by the electrochemical reaction mode, has advantages such as energy transformation ratio height, safe and reliable, environmental protection, is a kind of eco-friendly new chemical energy.Proton Exchange Membrane Fuel Cells with solid-state PEM as electrolyte, except that advantage with general fuel cell, have also that but normal temperature starts fast, no electrolyte loss, life-span are long, specific power and the high outstanding advantage of specific energy, are called as the fuel cell in the 5th generation.Wherein DMFC (DMFC) be a kind of be the Proton Exchange Membrane Fuel Cells of fuel with the liquid methanol, have outstanding advantages such as the fuel cheapness is abundant, battery structure is simple, cost is low, be particularly useful for portable power source, become 21st century fuel cell technology development focus.
The PEM that is adopted among the DMFC is mainly the Nation series membranes of perfluoro sulfonic acid membrane such as Dupond company at present.At the hydrogen-oxygen fuel cell exploitation, though have higher proton conductivity, chemical stability, heat endurance and mechanical stability, methanol crossover is serious when being used for DMFC, has greatly limited further exploitation and the commercialization process of DMFC at first for this class film.The methyl alcohol penetrate PEM arrives negative electrode and the reaction of oxygen generation no current, reduces fuel availability on the one hand, causes catalyst poisoning on the other hand, forms mixed current potential at negative electrode, reduces cathode performance, thereby shortens the service life of battery greatly.In addition, perfluoro sulfonic acid membrane (the about 800$/m that costs an arm and a leg
2), also be a very important factor of restriction DMFC extensive use.Therefore, preparation features good methanol diffusion resistance, proton exchange membrane material cheaply are the important steps that the DMFC technology is applied.
The hybrid inorganic-organic PEM can improve the alcohol-rejecting ability of PEM owing to the adding of inorganic particulate.And when the zeolite granular that adds rigidity in semirigid shitosan prepares hybridized film,, reduce the alcohol-rejecting ability of hybridized film because the poor compatibility between organic facies and the inorganic particulate is forming bigger non-selective defective hole at the interface easily.Therefore improve the compatibility of shitosan and zeolite, improve the form of boundary, can improve the alcohol-rejecting ability of film effectively.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of shitosan and surface modified Y-type zeolite hybridization liquid separation film, with the shitosan and the surface modified Y-type zeolite hybridization film of this method preparation, methanol permeability is lower, can be used as the DMFC film.
The present invention is achieved through the following technical solutions.The preparation method of a kind of shitosan and surface modified Y-type zeolite hybridization liquid separation film is characterized in that may further comprise the steps:
The surface modification of 1 zeolite:
(1) NaY type zeolite being become particle diameter with ball mill grinding is the zeolite powder of 0.5～1 μ m, according to the ratio of 1.5～2g/L this zeolite powder is joined the NH that concentration is 1～2mol/L
4NO
3Solution at 75～85 ℃ of heating 12～24h that reflux down, filters out zeolite powder and spends deionised water and be neutral up to cleaning solution, at 110～120 ℃ of down dry 8～10h, generates h-type zeolites (HY) at 500 ℃ of following calcining at constant temperature 6h then;
(2) be to mix at 1: 2: 20 h-type zeolite and 3-aminopropyl triethoxysilane and toluene by mass ratio, at 105～110 ℃ of following stirring and refluxing reaction 24h, filter, and, obtain having amino y-type zeolite (NH 50～70 ℃ of dryings afterwards respectively with absolute ethyl alcohol and deionized water washing
2-Y);
(3) be to mix at 1: 2: 20 h-type zeolite and 3-mercaptopropyl trimethoxysilane and toluene by mass ratio, at 105～110 ℃ of following stirring and refluxing reaction 24h, filter, and respectively with absolute ethyl alcohol and deionized water washing, obtain having the y-type zeolite (HS-Y) of sulfydryl afterwards 50～70 ℃ of dryings, it is that oxidation 24h makes sulfydryl (SH) be oxidized to sulfonic acid group (SO in 30% the hydrogen peroxide that the zeolite (HS-Y) that will have a sulfydryl according to the ratio of 30g/L joins mass fraction
3H), filter out zeolite and, be dipped into the H of 1mol/L then according to the ratio of the 10g/L zeolite after with oxidation respectively with the washing of absolute ethyl alcohol and deionized water
2SO
42～3h is protonated fully in the solution, filters, and is neutral with absolute ethyl alcohol and deionized water washing up to cleaning solution respectively, is drying to obtain the y-type zeolite (HSO that has sulfonate radical at 50～70 ℃ afterwards
3-Y);
The preparation of 2 hybridized film:
(1) be 2%～3% acetic acid aqueous solution with the acetate mass concentration that is made into soluble in water, the NH that step 1 is made according to the ratio of 2～12g/L
2-y-type zeolite or HSO
3-y-type zeolite joins in the acetic acid solution, stirs with ultrasonic alternately dispersion and obtains suspension;
(2) according to the ratio of 20～30g/L shitosan is added in the suspension that step (1) makes, stir 2～3h dissolving down at 60～80 ℃, 20～25 ℃ of following dispersed with stirring obtain casting solution;
(3) the prepared casting solution of step (2) is filtered de-bubble, standing and defoaming 1～2h waters casting solution on glass plate drying and forming-film under 25 ℃ then;
(4) with the prepared dry film of step (3) at 2mol/L H
2SO
4Carry out crosslinked 24h in the aqueous solution, spend deionised water to cleaning solution after crosslinked and be neutral, obtain the sulfuric acid cross linking membrane;
(5) with sulfuric acid cross linking membrane 25 ℃ of dry 24h in vacuum drying chamber, volatilization removes and desolvates, and obtains the hybridized film of shitosan and surface modified Y zeolite.
The invention has the advantages that: the film preparation process is simple, and controllability is strong.Raw material sources are abundant, and are cheap, and system film cost is low.Prepared shitosan and surface modified Y-type zeolite hybridization film all have lower methanol permeability as the DMFC film in the methanol aqueous solution (2mol/L) of low concentration and intermediate concentration methanol aqueous solution (12mol/L).
The specific embodiment
Embodiment one
The average grain diameter that ball mill grinding was disperseed is that to add 700mL concentration be the NH of 1mol/L to the NaY type zeolite 1.5g of 1 μ m
4NO
3In the solution, at 80 ℃ of heating 24h that reflux down.Filter out zeolite and spend deionised water and be neutral, at 110 ℃ of dry 10h down up to cleaning solution.Generate h-type zeolite (HY) at 500 ℃ of following calcining at constant temperature 6h then.
The HY zeolite 1.0g that makes is joined in the mixed liquor of 3-aminopropyl triethoxysilane 2.0g and toluene 20g, at 110 ℃ of following stirring and refluxing reaction 24h, filter, spend deionised water 3 times for 2 times again with absolute ethanol washing earlier, 60 ℃ of following dryings obtain having amino y-type zeolite (NH
2-Y).
With 3.0g CH
3COOH is dissolved in the 150mL water, is mixed with mass fraction and is 2% CH
3The COOH aqueous solution, adding the 0.9g average grain diameter is the NH of 1 μ m
2-Y zeolite, with the rotating speed stirring 10min of 500r/min, the power ultrasonic with 160W disperses 10min then, obtains homodisperse suspension.Take by weighing the 3.0g shitosan and add in the suspension, the rotating speed with 500r/min in 80 ℃ of waters bath with thermostatic control stirs 2h, and dissolving obtains NH fully
2-Y zeolite content is the casting solution of 30wt%.Casting solution is continued to stir and ultrasonic dispersion 1h with the rotating speed of 500r/min, leave standstill 1h after the filtration and carry out deaeration, obtain evenly still casting solution.With casting solution curtain coating on glass plate, 25 ℃ of following drying and forming-films.In 200mL concentration the H of 2mol/L with diaphragm then
2SO
4Crosslinked 24h in the aqueous solution is washed till washing Industry with deionized water and is the neutral back 24h that soaks in deionized water.After the film taking-up, 25 ℃ of dry 24h make shitosan and NH in vacuum drying chamber
2-Y zeolite hybridization film (film 1).
Embodiment two
The average grain diameter that ball mill grinding was disperseed is that to add 700mL concentration be the NH of 1mol/L to the NaY type zeolite 1.5g of 1 μ m
4NO
3In the solution, at 80 ℃ of heating 24h that reflux down.Filter out zeolite and spend deionised water and be neutral, at 120 ℃ of dry 8h down up to cleaning solution.Generate h-type zeolite (HY) at 500 ℃ of following calcining at constant temperature 6h then.
The HY zeolite 1.5g that makes is joined in the mixed liquor of 3-aminopropyl triethoxysilane 3.0g and toluene 30g, at 110 ℃ of following stirring and refluxing reaction 24h, filter, spend deionised water 3 times for 2 times again with absolute ethanol washing earlier, 60 ℃ of following dryings obtain having amino y-type zeolite (NH
2-Y).
With 3.0g CH
3COOH is dissolved in the 150mL water, is mixed with mass fraction and is 2% CH
3The COOH aqueous solution, adding 1.2g grinding back average grain diameter is the NH of 1 μ m
2-Y zeolite disperses 10min with the power ultrasonic with 160W behind the rotating speed stirring 10min of 500r/min, obtains homodisperse suspension.Take by weighing the 3.0g shitosan and add in the suspension, stir 2h with 500r/min in 80 ℃ of waters bath with thermostatic control, dissolving obtains NH fully
2-Y zeolite content is the casting solution of 40wt%.Casting solution is continued to stir and ultrasonic dispersion 1h with the rotating speed of 500r/min, leave standstill 1h after the filtration and carry out deaeration, obtain evenly still casting solution.With casting solution curtain coating on glass plate, 25 ℃ of following drying and forming-films.In 200mL concentration the H of 2mol/L with diaphragm then
2SO
4Crosslinked 24h in the aqueous solution is washed till washing Industry with deionized water and is the neutral back 24h that soaks in deionized water.After the film taking-up, 25 ℃ of dry 24h make shitosan and NH in vacuum drying chamber
2-Y zeolite hybridization film (film 2).
Embodiment three
The average grain diameter that ball mill grinding was disperseed is that to add 700mL concentration be the NH of 1mol/L to the NaY type zeolite 1.5g of 1 μ m
4NO
3In the solution, at 80 ℃ of heating 24h that reflux down.Filter out zeolite and spend deionised water and be neutral, at 110 ℃ of dry 10h down up to cleaning solution.Generate h-type zeolite (HY) at 500 ℃ of following calcining at constant temperature 6h then.
The HY zeolite 1.5g that makes is joined in the mixed liquor of 3-aminopropyl triethoxysilane 3.0g and toluene 30g, at 110 ℃ of following stirring and refluxing reaction 24h, filter, spend deionised water 3 times for 2 times again with absolute ethanol washing earlier, 60 ℃ of following dryings obtain having the y-type zeolite (HS-Y) of sulfydryl.It is in 30% the hydrogen peroxide that zeolite (HS-Y) 1.5g that will have a sulfydryl joins the 50mL mass fraction, and oxidation 24h filters out zeolite and spends deionised water 3 times for 2 times again to neutrality with absolute ethanol washing earlier.Then the zeolite 1.5g after the oxidation is dipped into the H that 100mL concentration is 1mol/L
2SO
42h is protonated fully in the solution, filters, and spends deionised water 3 times for 2 times again to neutrality with absolute ethanol washing, and 60 ℃ are drying to obtain the y-type zeolite (HSO that has sulfonate radical
3-Y).
With 3.0g CH
3COOH is dissolved in the 150mL water, is mixed with the CH of mass fraction 2%
3The COOH aqueous solution, adding 0.9g grinding back average grain diameter is the HSO of 1 μ m
3-Y zeolite disperses 10min with the power ultrasonic with 160W behind the rotating speed stirring 10min of 500r/min, obtains homodisperse suspension.Take by weighing the 3.0g shitosan and add in the suspension, stir 2h with 500r/min in 80 ℃ of waters bath with thermostatic control, dissolving obtains HSO fully
3-Y zeolite content is the casting solution of 30wt%.Casting solution is continued to stir and ultrasonic dispersion 1h with the rotating speed of 500r/min, leave standstill 2h after the filtration and carry out deaeration, obtain evenly still casting solution.With casting solution in curtain coating on glass plate, 25 ℃ of following drying and forming-films.In 200mL concentration the H of 2mol/L with diaphragm then
2SO
4Crosslinked 24h in the aqueous solution is washed till neutral back with deionized water and soaks 24h in deionized water.After the film taking-up, 25 ℃ of dry 24h make shitosan and HSO in vacuum drying chamber
3-Y zeolite hybridization film (film 3).
Embodiment four
The average grain diameter that ball mill grinding was disperseed is that to add 700mL concentration be the NH of 1mol/L to the NaY type zeolite 1.5g of 1 μ m
4NO
3In the solution, at 80 ℃ of heating 24h that reflux down.Filter out zeolite and spend deionised water and be neutral, at 120 ℃ of dry 8h down up to cleaning solution.Generate h-type zeolite (HY) at 500 ℃ of following calcining at constant temperature 6h then.
The HY zeolite 1.5g that makes is joined in the mixed liquor of 3-aminopropyl triethoxysilane 3.0g and toluene 30g, at 110 ℃ of following stirring and refluxing reaction 24h, filter, spend deionised water 3 times for 2 times again with absolute ethanol washing earlier, 60 ℃ of following dryings obtain having the y-type zeolite (HS-Y) of sulfydryl.Zeolite (HS-Y) 1.5g that will have sulfydryl joins in the hydrogen peroxide of 50mL mass fraction 30%, and oxidation 24h makes sulfydryl (SH) be oxidized to sulfonic acid group (SO
3H), filter and wash 3 times with absolute ethanol washing 2 times and deionized water respectively.Then the zeolite 1.5g after the oxidation is dipped into the H that 100mL concentration is 1mol/L
2SO
42h is protonated fully in the solution, filters, and spends deionised water 3 times for 2 times again to neutrality with absolute ethanol washing, and 60 ℃ are drying to obtain the y-type zeolite (HSO that has sulfonate radical
3-Y).
With 3.0g CH
3COOH is dissolved in the 150mL water, is mixed with the CH of mass fraction 2%
3The COOH aqueous solution, adding 1.2g grinding back average grain diameter is the HSO of 1 μ m
3-Y zeolite disperses 10min with the power ultrasonic with 160W behind the rotating speed stirring 10min of 500r/min, obtains homodisperse suspension.Take by weighing the 3.0g shitosan and add in the suspension, stir 2h with 500r/min in 80 ℃ of waters bath with thermostatic control, dissolving obtains HSO fully
3-Y zeolite content is the casting solution of 40wt%.Casting solution is continued to stir and ultrasonic dispersion 1h with the rotating speed of 500r/min, leave standstill 2h after the filtration and carry out deaeration, obtain evenly still casting solution.With casting solution in curtain coating on glass plate, 25 ℃ of following drying and forming-films.In 200mL concentration the H of 2mol/L with diaphragm then
2SO
4Crosslinked 24h in the aqueous solution is washed till neutral back with deionized water and soaks 24h in deionized water.After the film taking-up, 25 ℃ of dry 24h make shitosan and HSO in vacuum drying chamber
3-Y zeolite hybridization film (film 4).
Comparative Examples one
With 3.0g CH
3COOH is dissolved in the 150mL water, is mixed with the CH of mass fraction 2%
3The COOH aqueous solution adds the 3.0g shitosan, and the rotating speed with 500r/min in 80 ℃ of waters bath with thermostatic control stirs 2h, fully dissolving.Casting solution is proceeded to stir and ultrasonic dispersion 1h, leave standstill 1h after the filtration and carry out deaeration, obtain evenly still casting solution.With casting solution curtain coating on glass plate, 25 ℃ of following drying and forming-films.In 200mL concentration the H of 2mol/L with diaphragm then
2SO
4Crosslinked 24h in the aqueous solution is washed till neutral back with deionized water and soaks 24h in deionized water.After the film taking-up, 25 ℃ of dry 24h in vacuum drying chamber make pure chistosan film (film 5).
Comparative Examples two
With 3.0g CH
3COOH is dissolved in the 150mL water, is mixed with into the CH of mass fraction 2%
3The COOH aqueous solution, adding 0.9g grinding back average grain diameter is the NaY zeolite of 1 μ m, disperses 10min with the power ultrasonic with 160W behind the rotating speed stirring 10min of 500r/min, obtains homodisperse suspension.Take by weighing the 3.0g shitosan and add in the suspension, the rotating speed with 500r/min in 80 ℃ of waters bath with thermostatic control stirs 2h, and dissolving obtains the casting solution that the NaY zeolite content is 30wt% fully.Casting solution is continued to stir and ultrasonic dispersion 1h with the rotating speed of 500r/min, leave standstill 1h after the filtration and carry out deaeration, obtain evenly still casting solution.With casting solution in curtain coating on glass plate, 25 ℃ of following drying and forming-films.In 200mL concentration the H of 2mol/L with diaphragm then
2SO
4Crosslinked 24h in the aqueous solution is washed till neutral back with deionized water and soaks 24h in deionized water.After the film taking-up, 25 ℃ of dry 24h in vacuum drying chamber make shitosan and NaY type zeolite hybridization film (film 6).
Comparative Examples three
With 3.0g CH
3COOH is dissolved in the 150mL water, is mixed with the CH of mass fraction 2%
3The COOH aqueous solution, adding 1.2g grinding back average grain diameter is the NaY zeolite of 1 μ m, disperses 10min with the power ultrasonic with 160W behind the rotating speed stirring 10min of 500r/min, obtains homodisperse suspension.Take by weighing the 3.0g shitosan and add in the suspension, the rotating speed with 500r/min in 80 ℃ of waters bath with thermostatic control stirs 2h, and dissolving obtains the casting solution that the NaY zeolite content is 40wt% fully.Casting solution is continued to stir and ultrasonic dispersion 1h with the rotating speed of 500r/min, leave standstill 1h after the filtration and carry out deaeration, obtain evenly still casting solution.With casting solution in curtain coating on glass plate, 25 ℃ of following drying and forming-films.In 200mL concentration the H of 2mol/L with diaphragm then
2SO
4Crosslinked 24h in the aqueous solution is washed till neutral back with deionized water and soaks 24h in deionized water.After the film taking-up, 25 ℃ of dry 24h in vacuum drying chamber make shitosan and NaY type zeolite hybridization film (film 7).
Table 1 is depicted as in embodiment and the Comparative Examples prepared film respectively in 2mol/L and 12mol/L methanol aqueous solution, the methanol permeability data.
Table 1
| Numbering | Zeolite type | Zeolite quality (wt%) | Methanol permeability/2mol/L (10 -6cm 2/s) | Methanol permeability/12mol/L (10 -7cm 2/s) |
| Film 1 film 2 films 3 films 4 films 5 films 6 films 7 | NH 2-Y NH 2-Y HSO 3-Y HSO 3-Y NaY NaY NaY | 30 40 30 40 0 30 40 | 1.14 1.03 0.96 0.90 2.13 1.18 1.15 | 5.65 5.13 4.31 3.90 8.79 7.21 6.82 |
As can be seen from Table 1, than the hybridized film of blank chitosan film and shitosan and the preparation of NaY zeolite, be that methanol permeability in the methanol aqueous solution of 2mol/L and 12mol/L has had tangible reduction in concentration by the hybridized film of surface remodeling y-type zeolite and Chitosan Preparation.Wherein by HSO
3The zeolite content of-y-type zeolite and Chitosan Preparation is that the methanol permeability of 40% hybridized film is minimum.
Claims (1)
1. the preparation method of shitosan and surface modified Y-type zeolite hybridization liquid separation film is characterized in that may further comprise the steps:
1) surface modification of zeolite:
(1) NaY type zeolite being become particle diameter with ball mill grinding is the zeolite powder of 0.5～1 μ m, according to the ratio of 1.5～2g/L this zeolite powder is joined the NH that concentration is 1～2mol/L
4NO
3Solution 75～85 ℃ of heating 12～24 hours that reflux down, filters out zeolite powder and spends deionised water and be neutral up to cleaning solution, then 110～120 ℃ dry 8～10 hours down, generated h-type zeolite in 6 hours 500 ℃ of following calcining at constant temperature;
(2) be to mix at 1: 2: 20 h-type zeolite and 3-aminopropyl triethoxysilane and toluene by mass ratio, 105～110 ℃ of following stirring and refluxing reactions 24 hours, filter, and, obtain having amino y-type zeolite 50～70 ℃ of dryings afterwards respectively with absolute ethyl alcohol and deionized water washing;
(3) be to mix at 1: 2: 20 h-type zeolite and 3-mercaptopropyl trimethoxysilane and toluene by mass ratio, 105～110 ℃ of following stirring and refluxing reactions 24 hours, filter, and respectively with absolute ethyl alcohol and deionized water washing, obtain having the y-type zeolite of sulfydryl afterwards 50～70 ℃ of dryings, it is in 30% the hydrogen peroxide that the zeolite that will have a sulfydryl according to the ratio of 30g/L joins mass fraction, oxidation 24 hours, making sulfhydryl oxidase is sulfonic acid group, filter out zeolite and respectively with the washing of absolute ethyl alcohol and deionized water, be dipped into the H of 1mol/L then according to the ratio of the 10g/L zeolite after with oxidation
2SO
4In the solution 2～3 hours protonated fully, filter, be neutrality with absolute ethyl alcohol and deionized water washing up to cleaning solution respectively, be drying to obtain the y-type zeolite that has sulfonate radical at 50～70 ℃ afterwards;
2) preparation of hybridized film:
(1) be 2%～3% acetic acid aqueous solution with the acetate mass concentration that is made into soluble in water, the NH that step 1) is made according to the ratio of 2～12g/L
2-y-type zeolite or HSO
3-y-type zeolite joins in the acetic acid solution, stirs with ultrasonic alternately dispersion and obtains suspension;
(2) according to the ratio of 20～30g/L shitosan is added in the suspension that step (1) makes, stir dissolving in 2～3 hours down at 60～80 ℃, 20～25 ℃ of following dispersed with stirring obtain casting solution;
(3) the prepared casting solution of step (2) is filtered de-bubble, standing and defoaming is 1～2 hour then, casting solution is watered on glass plate drying and forming-film under 25 ℃;
(4) with the prepared dry film of step (3) at 2mol/L H
2SO
4Carried out in the aqueous solution crosslinked 24 hours, and spent deionised water to cleaning solution after crosslinked and be neutral, obtain the sulfuric acid cross linking membrane;
(5) with sulfuric acid cross linking membrane 25 ℃ of dryings 24 hours in vacuum drying chamber, volatilization removes and desolvates, and obtains the hybridized film of shitosan and surface modified Y zeolite.
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| CN101518719B (en) * | 2008-02-29 | 2012-02-01 | 中国科学院过程工程研究所 | Method for preparing organic-inorganic hybrid evaporation alcohol permselective membrane |
| CN101623603B (en) * | 2008-05-21 | 2015-11-25 | 霍尼韦尔国际公司 | Recycle the system and method for nano ceramics |
| CN103241960A (en) * | 2013-05-10 | 2013-08-14 | 安徽工业大学 | Hydrophobic moistureproof surface modification method for hollow glass beads |
| CN104415668A (en) * | 2013-08-20 | 2015-03-18 | 中国科学院大连化学物理研究所 | Making method of organic-inorganic hybrid separating membrane |
| CN104857861B (en) * | 2015-04-24 | 2017-06-06 | 南京工业大学 | Preparation method of ceramic composite membrane for anionic dye desalination |
| CN104857861A (en) * | 2015-04-24 | 2015-08-26 | 南京工业大学 | Preparation method of ceramic composite membrane for anionic dye desalination |
| CN106356548A (en) * | 2016-11-28 | 2017-01-25 | 哈尔滨工业大学深圳研究生院 | Modification method for proton exchange membrane of direct methanol fuel cell |
| CN106356548B (en) * | 2016-11-28 | 2019-05-10 | 哈尔滨工业大学深圳研究生院 | A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell |
| CN110975927A (en) * | 2019-12-17 | 2020-04-10 | 万华化学集团股份有限公司 | Zone-limited bimetallic spherical catalyst and preparation method and application thereof |
| CN110975927B (en) * | 2019-12-17 | 2022-08-05 | 万华化学集团股份有限公司 | Zone-limited bimetallic spherical catalyst and preparation method and application thereof |
| CN111394891A (en) * | 2020-03-25 | 2020-07-10 | 武汉理工大学 | Preparation method of chitosan oligosaccharide and polyester composite material |
| CN115007000A (en) * | 2021-12-02 | 2022-09-06 | 淮阴师范学院 | Modified attapulgite polylactic acid separation membrane, preparation method and application |
| CN115007000B (en) * | 2021-12-02 | 2023-08-18 | 淮阴师范学院 | Modified attapulgite polylactic acid separation membrane, preparation method and application |
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