CN104906966A - Cellulose acetate/functionalized graphene mixed media hollow fiber positive osmotic membrane - Google Patents
Cellulose acetate/functionalized graphene mixed media hollow fiber positive osmotic membrane Download PDFInfo
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- CN104906966A CN104906966A CN201510245504.4A CN201510245504A CN104906966A CN 104906966 A CN104906966 A CN 104906966A CN 201510245504 A CN201510245504 A CN 201510245504A CN 104906966 A CN104906966 A CN 104906966A
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Abstract
The invention discloses a cellulose acetate/functionalized graphene mixed media hollow fiber positive osmotic membrane. 0.05-3.0% (w/w) of graphene is added into a solution composed of N-methyl-pyrrolidone or dimethylacetamide or dimethylformamide and 1,4-dioxane, 2.0-20.0% (w/w) of a polyethylene glycol or polyvinylpyrrolidone/lithium chloride composite additive with a volume ratio of 7:1 is added, stirring is carried out for 15-60min, then 10.0-35.0% (w/w) of cellulose acetate is added, stirring is carried out, the mixture is allowed to stand, and a casting film solution. The casting film solution is squeezed into an annular gap of a nozzle, goes through an air gap of 2-20cm, and goes into deionized water with a temperature of 20-60 DEG C, solidification is carried out, and a positive osmotic membrane is obtained after washing. When 1M of NaCl is employed as a drive liquid and deionized water is employed as a raw material liquid, the water flux is 18.3L/m2h, the reverse salt flux is less than 3.3g/m2h, and the contact angle is 57.5 degrees.
Description
Technical field
The present invention relates to technical field of membrane, be specially a kind of with the doughnut forward osmosis membrane of cellulose acetate membrane material and the blended preparation of functionalization graphene.
Background technology
China is a populous nation, also more to the demand of water resource, and water consumption deficiency becomes the key subjects that people pay close attention to already per capita.In recent years, along with the growth of world population and the develop rapidly of social and economic condition, day by day increase the demand of water, it is more and more serious that the phenomenon that water resource is weary relative to plaque also becomes, in some areas, shortage of water resources has become one of major reason threatening human survival and economic development.It is reported have 1,200,000,000 people to lack safety, clean drinking water at present in the world.The economic loss caused because of shortage of water resources and quality problem every year in African Territories, up to 28,000,000,000, accounts for 5% of African GDP.
Water and the energy inseparable with everyone existence, as a kind of emerging technology, forward osmosis membrane water resource utilize and production of energy in all demonstrate huge potentiality.Just permeate (forward osmosis, FO) be a kind of membrane separation technique relying on film both sides osmotic pressure to drive, just day by day come into one's own, relevant Theory and applications research achieves larger progress, has been successfully applied to the fields such as desalinization, wastewater treatment, food medicine, the energy.Desirable forward osmosis membrane should have following characteristics: (1) fine and close, the cortex of low porosity, high salt-stopping rate; (2) cortex of film has good hydrophily, higher water flux; (3) supporting layer of film is as far as possible thin, and porosity is high; (4) alap interior concentration polarization; (5) higher mechanical strength; (6) higher resistance to chemical corrosion.These all with the material character of forward osmosis membrane and the structure of film closely related, membrane material and the forward osmosis membrane preparation method of visible function admirable are particularly important.Through development in recent years, forward osmosis membrane has been widely used in the multiple fields such as desalinization, sewage disposal, food processing, medicine, and show excellent performance, but the research of China's forward osmosis membrane is still in the elementary step at present, therefore, to have more high performance forward osmosis membrane of far-reaching significance in development.
Membrane material is the core of whole positive permeability and separation process, comparatively large to the performance impact of forward osmosis membrane, therefore how to select suitable membrane material to be all the focus that people pay close attention to all the time.Generally, any densification, selective permeable material that hydrophily is good can use as forward osmosis membrane.Polyether sulfone, polyamide, cellulose diacetate, Triafol T etc. are all the material of preparing the most often used.Wherein, cellulose acetate series products the most often uses.The forward osmosis membrane that HTI company uses cellulose acetate and Triafol T to prepare has entered the commercial applications stage at present, these films have and good retain characteristic, but the water flux measured when drawing liquid with the sodium chloride solution of 2M is often less than 20 L/m
2h.The people such as the Rui Chin Ong of NUS have prepared novel cellulose product.By carrying out the modification such as hydroxylating, carboxylated to traditional cellulosic material, thus prepared forward osmosis membrane is made to have higher water flux and salt interception.In order to prepare the forward osmosis membrane of higher water flux, sight turns to and prepares composite flat membrane by interfacial polymerization by many researchers.This flat compound forward osmosis membrane uses the material with loose structure as polysulfones, polyether sulfone/polysulfones etc. usually.But nearest research finds, the performance that membrane pollution problem and concentration polarization phenomenon have a strong impact on forward osmosis membrane further develops with it, therefore there has been proposed many methods and carries out modification to film.
Research shows, is improved that the capability operation of forward osmosis membrane is simple, effect better by blend method, therefore causes people more and more to pay close attention to.The additive the most often used has inorganic additive and organic additive two kinds, wherein, is seen everywhere as additive about utilizing CNT, silica, magnetic Nano material etc. to the report that film carries out modification.The selection of additive types is most important.First, selected additive must have good compatibility with polymer; Secondly, additive particles abundant mixing in the polymer is also vital.
Graphene (Graphene Oxide, GO) be the one that it is found that by carbon atom with sp
2hydridization is formed, there is monoatomic layer, the atomic crystal of bi-dimensional cellular shape structure.In Graphene, except purely introducing except the peroxide bridge of oxygen atom, in structure, also there are other kind functional groups, such as carbonyl (=CO), hydroxyl (-OH) and phenolic hydroxyl group, making Graphene have extremely strong hydrophily and fabulous biocidal property.And the chemical reaction between these groups and polyamine, multi-anhydride, polyalcohol, multicomponent isocyanate molecule can be utilized to carry out covalent bond functionalization to graphenic surface, the physical and chemical performance of further raising Graphene, itself and acetyl cellulose blend are prepared forward osmosis membrane, be expected to the forward osmosis membrane of the high water flux of excellent, stain resistance and biocidal property, this is that the research and development of forward osmosis membrane material and application provide new thinking.
How while obtaining excellent hydrophilic, make again forward osmosis membrane have resistance tocrocking and keep the stability of water flux, this is the film scientific worker difficult problem thinking always and studying in recent years.The present invention adopts functionalization graphene to prepare doughnut forward osmosis membrane, improves structure and the hydrophily of forward osmosis membrane, there is not yet bibliographical information both at home and abroad.
Summary of the invention
The invention discloses a kind of cellulose acetate/functionalization graphene mixed-matrix doughnut forward osmosis membrane, adopt following methods to make:
Consisting of of cellulose acetate/functionalization graphene mixed-matrix doughnut forward osmosis membrane casting solution: cellulose acetate 10.0% ~ 35.0%(w/w), additive is organic/inorganic compound additive, as polyethylene glycol/lithium chloride compound additive or polyvinylpyrrolidone/lithium chloride compound additive 2.0 ~ 20.0%(w/w) (volume ratio is polyethylene glycol or polyvinylpyrrolidone: lithium chloride=7:1), functionalization graphene 0.05% ~ 3.0%(w/w), all the other are 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide and 1, the mixed solvent of 4-dioxane, its volume ratio is 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide: 1, 4-dioxane=1:0.2 ~ 10.0.
First functionalization graphene is joined 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide and 1, in the mixed solvent of 4-dioxane, utilize the ultrasonic functionalization graphene that makes dispersed wherein, according to a certain percentage additive is joined in dissolving tank subsequently, add cellulose acetate after uniform stirring 15 ~ 60 min, fully stir and leave standstill at 20 ~ 80 DEG C of temperature and obtain casting solution.
Then, by the casting solution that obtains static 8 ~ 24 hours at the reaction temperatures, bubble remaining in casting solution is removed;
Casting solution in batch can is squeezed in the annular space of shower nozzle by measuring pump under 0.05 ~ 0.5MPa pressure, meanwhile, interior coagulating bath enters into the Inserting Tube of shower nozzle by constant flow pump, enter into the outer coagulating basin that 20 DEG C ~ 60 DEG C of deionized waters are housed after the as-spun fibre formed leaves shower nozzle to solidify through 2 ~ 20cm the air gap, by the doughnut extruded from spinneret after coagulating bath is fully solidified, doughnut forward osmosis membrane is collected by spiral filament forming machine, prepared hollow-fibre membrane is put into deionized water and is rinsed 48 hours, within 8 ~ 12 hours, change a water, deionized water is cleaned and is namely obtained cellulose acetate/functionalization graphene mixed-matrix doughnut forward osmosis membrane.
The forward osmosis membrane of the invention described above, preferred: described solvent N-methyl pyrilidone or dimethylacetylamide or dimethyl formamide and 1, the mixed solvent of 4-dioxane, volume ratio is 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide: Isosorbide-5-Nitrae-dioxane=1:0.2 ~ 10.0.
The forward osmosis membrane of the invention described above, preferred: described pore-foaming agent is organic/inorganic compound additive, and as polyethylene glycol/lithium chloride compound additive or polyvinylpyrrolidone/lithium chloride compound additive, ratio is 2.0 ~ 20.0%(w/w).
The forward osmosis membrane of the invention described above, preferred: the temperature of coagulating bath is 20 DEG C ~ 60 DEG C; After as-spun fibre leaves shower nozzle through the air gap height be 2 ~ 20cm.
The forward osmosis membrane of the invention described above, preferred: described Graphene be by covalency process give that Graphene polyamine or multi-anhydride or polyalcohol active function groups generate grapheme modified.
The forward osmosis membrane of the invention described above, preferred: consisting of of forward osmosis membrane formula of casting: cellulose acetate 10.0% ~ 35.0%(w/w), additive 2.0 ~ 20.0%(w/w), functionalization graphene 0.05% ~ 3.0%(w/w); 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide: Isosorbide-5-Nitrae-dioxane=1:0.2 ~ 10.0.
The hydrophilicity that product utilization functionalization graphene of the present invention is excellent and stain resistance, effectively can improve the performance of doughnut forward osmosis membrane.By controlling the cellulose acetate of casting solution, pore-foaming agent, the content of functionalization graphene and the index such as the kind of mixed solvent and ratio, the pure water infiltration coefficient of controlling diaphragm, stain resistance and stable sex expression.
This doughnut forward osmosis membrane product has the advantages such as stain resistance, unit volume membrane area and flux are large.In addition, mixed-matrix forward osmosis membrane spinning properties of the present invention is good, is spun to that membrane process technique is simple, cost is low.
detailed description of the invention:
embodiment 1:
First by 1.0%(w/w) functionalization graphene joins 63.0%(w/w) 1-METHYLPYRROLIDONE and 1,4-dioxane (1-METHYLPYRROLIDONE and 1, the volume ratio of 4-dioxane is 1:0.8) mixed solvent in, utilize the ultrasonic functionalization graphene that makes dispersed wherein, subsequently by 6.0%(w/w) polyethylene glycol/lithium chloride compound additive (volume ratio is 7:1) joins in dissolving tank, add 30% cellulose acetate after uniform stirring 5 min, fully stir and leave standstill at 60 DEG C of temperature and obtain casting solution.
Then, by the casting solution that obtains static 24 hours at the reaction temperatures, bubble remaining in casting solution is removed;
Casting solution in batch can is squeezed in the annular space of shower nozzle by measuring pump under 0.05 ~ 0.5MPa pressure; Meanwhile, interior coagulating bath enters into the Inserting Tube of shower nozzle by constant flow pump, enter into the outer coagulating basin that 30 DEG C of deionized waters are housed after the as-spun fibre formed leaves shower nozzle to solidify through 5cm the air gap, by the doughnut extruded from spinneret after coagulating bath is fully solidified, hollow-fibre membrane is collected by spiral filament forming machine, prepared hollow-fibre membrane is put into deionized water and is rinsed 48 hours, obtains the blended doughnut forward osmosis membrane of cellulose acetate/functionalization graphene.The forward osmosis membrane obtained utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 18.3L/m
2more than h, reverse flux salt is less than 3.3g/m
2h, surface contact angle is 57.5 °.
embodiment 2:
The ratio of functionalization graphene, cellulose acetate is adjusted to 3.0%(w/w), 28.0%(w/w), remaining is with embodiment 1.The forward osmosis membrane obtained utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 19.5L/m
2more than h, reverse flux salt is less than 4.1g/m
2h, surface contact angle is 56.3 °.
embodiment 3:
The ratio of polyethylene glycol/lithium chloride compound additive is adjusted to 10.0%(w/w), the volume ratio that the ratio of mixed solvent is adjusted to 59.0%(N-methyl pyrrolidone and Isosorbide-5-Nitrae-dioxane is adjusted to 1:2.0), remaining is with embodiment 1.The forward osmosis membrane obtained utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 18.7L/m
2more than h, the little 4.5g/m of reverse flux salt
2h, surface contact angle is 57.8 °.
embodiment 4:
The ratio of cellulose acetate is adjusted to 20.0%(w/w), the volume ratio that the ratio of mixed solvent is adjusted to 73.0%(N-methyl pyrrolidone and Isosorbide-5-Nitrae-dioxane is adjusted to 1:1.0), remaining is with embodiment 1.The forward osmosis membrane obtained utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 21.3L/m
2more than h, reverse flux salt is less than 5.7g/m
2h, surface contact angle is 56.2 °.
embodiment 5:
Coagulation bath temperature is adjusted to 60 DEG C, after as-spun fibre leaves shower nozzle through the air gap Height Adjustment be 20cm, remaining is with embodiment 1.The forward osmosis membrane obtained utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 15.9L/m
2more than h, reverse flux salt is less than 3.7g/m
2h, surface contact angle is 56.6 °.
comparative example 1:
By 30%(W/W) cellulose acetate, 6.0%(w/w) polyethylene glycol/lithium chloride compound additive joins 1-METHYLPYRROLIDONE and 1, in 4-dioxane mixed solvent (dimethyl formamide: acetone=1:0.8), be stirred to full and uniform at 60 DEG C of temperature; Then, by the casting solution that obtains static 24 hours at the reaction temperatures, bubble remaining in casting solution is removed; Casting solution in batch can is squeezed in the annular space of shower nozzle by measuring pump under 0.05 ~ 0.5MPa pressure; Meanwhile, interior coagulating bath enters into the Inserting Tube of shower nozzle by constant flow pump, enter into the outer coagulating basin that 30 DEG C of deionized waters are housed after the as-spun fibre formed leaves shower nozzle to solidify through 5cm the air gap, by the doughnut extruded from spinneret after coagulating bath is fully solidified, doughnut forward osmosis membrane is collected by spiral filament forming machine, prepared hollow-fibre membrane is put into deionized water and is rinsed 48 hours, obtains high-performance cellulose acetate/functionalization graphene mixed-matrix doughnut forward osmosis membrane.The forward osmosis membrane obtained utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 13.7L/m
2more than h, reverse flux salt is less than 6.5g/m
2h, surface contact angle is 65.2 °.
Claims (6)
1. cellulose acetate/functionalization graphene mixed-matrix doughnut forward osmosis membrane, is characterized in that adopting following methods to make:
Consisting of of cellulose acetate/functionalization graphene mixed-matrix doughnut forward osmosis membrane casting solution: cellulose acetate 10.0% ~ 35.0%(w/w), additive is organic/inorganic compound additive, as polyethylene glycol/lithium chloride compound additive or polyvinylpyrrolidone/lithium chloride compound additive 2.0 ~ 20.0%(w/w) (volume ratio is polyethylene glycol or polyvinylpyrrolidone: lithium chloride=7:1), functionalization graphene 0.05% ~ 3.0%(w/w), all the other are 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide and 1, the mixed solvent of 4-dioxane, its volume ratio is 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide: 1, 4-dioxane=1:0.2 ~ 10.0,
First functionalization graphene is joined 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide and 1, in the solvent of 4-dioxane composition, utilize the ultrasonic functionalization graphene that makes dispersed wherein, according to a certain percentage additive is joined in dissolving tank subsequently, add cellulose acetate after uniform stirring 15 ~ 60 min, fully stir and leave standstill at 20 ~ 80 DEG C of temperature and obtain casting solution;
Then, by the casting solution that obtains static 8 ~ 24 hours at the reaction temperatures, bubble remaining in casting solution is removed;
Casting solution in batch can is squeezed in the annular space of shower nozzle by measuring pump under 0.05 ~ 0.5MPa pressure; Meanwhile, interior coagulating bath enters into the Inserting Tube of shower nozzle by constant flow pump, enter into the outer coagulating basin that 20 DEG C ~ 60 DEG C of deionized waters are housed after the as-spun fibre formed leaves shower nozzle to solidify through 2 ~ 20cm the air gap, by the doughnut extruded from spinneret after coagulating bath is fully solidified, hollow-fibre membrane is collected by spiral filament forming machine, prepared hollow-fibre membrane is put into deionized water and is rinsed 48 hours, within 8 ~ 12 hours, change a water, deionized water is cleaned and is namely obtained cellulose acetate/functionalization graphene mixed-matrix doughnut forward osmosis membrane.
2. forward osmosis membrane according to claim 1, it is characterized in that described solvent N-methyl pyrilidone or dimethylacetylamide or dimethyl formamide and 1, the mixed solvent of 4-dioxane, volume ratio is 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide: Isosorbide-5-Nitrae-dioxane=1:0.2 ~ 10.0.
3. forward osmosis membrane according to claim 1, it is characterized in that: described pore-foaming agent is organic/inorganic compound additive, as polyethylene glycol/lithium chloride compound additive or polyvinylpyrrolidone/lithium chloride compound additive, ratio is 2.0 ~ 20.0%(w/w).
4. forward osmosis membrane according to claim 1, is characterized in that: the temperature of coagulating bath is 20 DEG C ~ 60 DEG C; After as-spun fibre leaves shower nozzle through the air gap height be 2 ~ 20cm.
5. forward osmosis membrane according to claim 1, is characterized in that: described Graphene be by covalency process give that Graphene polyamine or multi-anhydride or polyalcohol active function groups generate grapheme modified.
6. forward osmosis membrane according to claim 1, is characterized in that: consisting of of forward osmosis membrane formula of casting: cellulose acetate 10.0% ~ 35.0%(w/w), additive 2.0 ~ 20.0%(w/w), functionalization graphene 0.05% ~ 3.0%; 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide: Isosorbide-5-Nitrae-dioxane=1:0.2 ~ 10.0.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921034A (en) * | 2016-06-21 | 2016-09-07 | 北京林业大学 | Preparation and application of graphene oxide-modified cellulose acetate forward osmosis membrane |
| CN106902646A (en) * | 2017-02-22 | 2017-06-30 | 济南大学 | High performance flat formula forward osmosis membrane and preparation method based on aminated carbon nano tube |
| CN106902637A (en) * | 2017-02-22 | 2017-06-30 | 济南大学 | High performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube |
| CN106925138A (en) * | 2017-02-22 | 2017-07-07 | 济南大学 | High performance flat formula forward osmosis membrane and preparation method based on carboxylic carbon nano-tube |
| CN107837690A (en) * | 2017-12-14 | 2018-03-27 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework ZIF 8 |
| CN107983159A (en) * | 2017-12-29 | 2018-05-04 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on metal organic framework MIL-100 (Fe) |
| CN107983172A (en) * | 2017-12-13 | 2018-05-04 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-100 (Fe) |
| CN107998902A (en) * | 2017-12-13 | 2018-05-08 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-53 |
| CN108014652A (en) * | 2017-12-29 | 2018-05-11 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on MIL-101 (Cr)/GO |
| CN108014655A (en) * | 2017-12-14 | 2018-05-11 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on MIL-101 (Cr)/GO |
| CN108031304A (en) * | 2017-12-14 | 2018-05-15 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-101 (Cr) |
| CN108043244A (en) * | 2017-12-29 | 2018-05-18 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on metal organic framework MIL-101 (Cr) |
| CN108043245A (en) * | 2017-12-29 | 2018-05-18 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on metal organic framework MIL-53 (Fe) |
| CN109529623A (en) * | 2018-10-31 | 2019-03-29 | 中国科学院重庆绿色智能技术研究院 | A kind of high-intensity high-throughput antibacterial forward osmosis membrane of no fabric and preparation method thereof |
| CN114887504A (en) * | 2022-06-21 | 2022-08-12 | 济南大学 | Flat plate type mixed matrix forward osmosis membrane based on ZIF-67 and preparation method thereof |
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2015
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921034A (en) * | 2016-06-21 | 2016-09-07 | 北京林业大学 | Preparation and application of graphene oxide-modified cellulose acetate forward osmosis membrane |
| CN106902646A (en) * | 2017-02-22 | 2017-06-30 | 济南大学 | High performance flat formula forward osmosis membrane and preparation method based on aminated carbon nano tube |
| CN106902637A (en) * | 2017-02-22 | 2017-06-30 | 济南大学 | High performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube |
| CN106925138A (en) * | 2017-02-22 | 2017-07-07 | 济南大学 | High performance flat formula forward osmosis membrane and preparation method based on carboxylic carbon nano-tube |
| CN107998902B (en) * | 2017-12-13 | 2020-01-10 | 济南大学 | Flat plate type mixed matrix forward osmosis membrane based on metal organic framework MIL-53 and preparation method |
| CN107983172A (en) * | 2017-12-13 | 2018-05-04 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-100 (Fe) |
| CN107998902A (en) * | 2017-12-13 | 2018-05-08 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-53 |
| CN108014655B (en) * | 2017-12-14 | 2019-10-01 | 济南大学 | Based on the flat mixed-matrix forward osmosis membrane of MIL-101 (Cr)/GO and preparation method |
| CN107837690A (en) * | 2017-12-14 | 2018-03-27 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework ZIF 8 |
| CN108014655A (en) * | 2017-12-14 | 2018-05-11 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on MIL-101 (Cr)/GO |
| CN108031304A (en) * | 2017-12-14 | 2018-05-15 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-101 (Cr) |
| CN108014652A (en) * | 2017-12-29 | 2018-05-11 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on MIL-101 (Cr)/GO |
| CN108043245A (en) * | 2017-12-29 | 2018-05-18 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on metal organic framework MIL-53 (Fe) |
| CN108043244A (en) * | 2017-12-29 | 2018-05-18 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on metal organic framework MIL-101 (Cr) |
| CN108014652B (en) * | 2017-12-29 | 2019-10-01 | 济南大学 | Based on MIL-101 (Cr)/GO acetyl cellulose blend doughnut forward osmosis membrane |
| CN107983159A (en) * | 2017-12-29 | 2018-05-04 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on metal organic framework MIL-100 (Fe) |
| CN109529623A (en) * | 2018-10-31 | 2019-03-29 | 中国科学院重庆绿色智能技术研究院 | A kind of high-intensity high-throughput antibacterial forward osmosis membrane of no fabric and preparation method thereof |
| CN114887504A (en) * | 2022-06-21 | 2022-08-12 | 济南大学 | Flat plate type mixed matrix forward osmosis membrane based on ZIF-67 and preparation method thereof |
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