CN104906967A - Cellulose acetate/nano titanium dioxide mixed media hollow fiber positive osmotic membrane - Google Patents
Cellulose acetate/nano titanium dioxide mixed media hollow fiber positive osmotic membrane Download PDFInfo
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- CN104906967A CN104906967A CN201510245514.8A CN201510245514A CN104906967A CN 104906967 A CN104906967 A CN 104906967A CN 201510245514 A CN201510245514 A CN 201510245514A CN 104906967 A CN104906967 A CN 104906967A
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- osmosis membrane
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Abstract
The invention discloses a cellulose acetate/nano titanium dioxide mixed media hollow fiber positive osmotic membrane. 0.05-4.0% (w/w) of nano titanium dioxide and 0.01-1.0% (w/w) of oxidized graphene are added into a solution composed of N-methyl-pyrrolidone or dimethylacetamide or dimethylformamide and 1,4-dioxane, 3.0-21.0% (w/w) of additives is added, uniform stirring is carried out for 5-60min, then 15.0-40.0% (w/w) of cellulose acetate is added, full stirring is carried out at a temperature of 20-70 DEG C, the mixture is allowed to stand, and a hollow fiber positive osmotic membrane is obtained through spinning. The osmotic membrane employs 1M of NaCl as a drive liquid and deionized water as a raw material liquid, the water flux is 16.5L/m2h, the reverse salt flux is less than 3.5g/m2h, and the contact angle is 60.2 degrees in test time of 1h.
Description
Technical field
The present invention relates to technical field of membrane, especially relate to the technology of preparing of organic-nano particle mixed-matrix hollow-fibre membrane, be specially a kind of mixed-matrix doughnut forward osmosis membrane prepared with cellulose acetate membrane material and nanometer titanium dioxide blending.
Background technology
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, the phenomenon that water resource is weary relative to plaque is also more and more serious, 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.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.
Just permeate (forward osmosis, FO) refer to that the throughout curve permeable membrane that then water can be spontaneous flows to the lower side of osmotic pressure (drawing liquid) from the side (material liquid) that osmotic pressure is higher at two kinds of different solution of the selective placement of the both sides through film osmotic pressure.The film prepared by positive penetration theory is used namely to be called forward osmosis membrane.Two aspects are mainly concentrated at present to the research of forward osmosis membrane, the selection of membrane material and draw choosing of liquid.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, hydrophily is good selective through material 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.Common forward osmosis membrane preparation method has interfacial polymerization, two selection tunic preparation method and NF membrane modification three kinds.In positive osmosis composite membrane prepared by interfacial polymerization, concentration polarization is more serious; Two selection tunic effectively reduces interior concentration polarization, but preparation technology is comparatively complicated; NF membrane Modified Membrane to the rejection of monovalent salt and water flux all lower; Therefore, need to develop new forward osmosis membrane preparation technology to improve the separating property of forward osmosis membrane.
Nano titanium oxide (nTiO
2) be a kind of amphoteric oxide of white powder, its particle size only has 10 to 50nm.Due to transparency and the UV protection function of its high unity, nano titanium oxide is obtained for application in a lot of field, such as: plastic products, wood preservation and fine ceramics.Nano titanium oxide as a kind of new material be applied to film field to reduce the pollution of film be because it can degrade gas chromatography and have microbe killing properties can; In addition, nano titanium oxide has larger specific area and good hydrophilicity.It is combined with cellulose acetate and prepares mixed-matrix doughnut forward osmosis membrane, be expected to while the high water flux of acquisition, also make forward osmosis membrane product have 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 hydrophilic nmature, 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 nano titanium oxide to prepare hollow-fibre 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/nano titanium oxide mixed-matrix doughnut forward osmosis membrane, adopt following methods to make:
By 0.05% ~ 4.0%(w/w) nano titanium oxide, 0.01% ~ 1.0%(w/w) graphene oxide joins 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide and 1, in the solvent of 4-dioxane composition, utilize and ultrasonicly make nano titanium oxide full and uniform dispersion wherein, subsequently by 3.0 ~ 21.0%(w/w) additive joins in dissolving tank, 15.0% ~ 40.0%(w/w is added after uniform stirring 5 ~ 60 min) cellulose acetate, fully stirs and leaves standstill and obtain casting solution at 20 ~ 70 DEG C of temperature; 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; Enter into the outer coagulating basin that 20 DEG C ~ 70 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, deionized water is cleaned and is namely obtained cellulose acetate/nano titanium oxide 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: Isosorbide-5-Nitrae-dioxane=1:0.2 ~ 10.0.
The forward osmosis membrane of the invention described above, preferred: the temperature of described coagulating bath is 20 DEG C ~ 70 DEG C.
The forward osmosis membrane of the invention described above, preferred: described nano titanium oxide is that anatase titanium dioxide combines with rutile-type, and particle diameter is 20-50nm.
The forward osmosis membrane of the invention described above, preferred: described forward osmosis membrane formula of casting: cellulose acetate 15.0% ~ 40.0%(w/w), pore-foaming agent 3.0 ~ 21.0%(w/w), nano titanium oxide 0.05% ~ 4.0%(w/w), Graphene 0.01% ~ 1.0%(w/w), dimethyl formamide or dimethylacetylamide or 1-METHYLPYRROLIDONE: Isosorbide-5-Nitrae-dioxane=1: 0.2 ~ 10.0.
The hydrophilicity that product utilization nano titanium oxide 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 nano titanium oxide and index, the pure water infiltration coefficient of controlling diaphragm and the size of reverse flux salt, stain resistance and the stable sex expression such as the kind of mixed solvent and ratio.
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 doughnut 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:
By 2.0%(w/w) nano titanium oxide, 0.1%(w/w) graphene oxide joins 55.9%(w/w) 1-METHYLPYRROLIDONE and 1,4-dioxane (1-METHYLPYRROLIDONE: 1,4-dioxane=1:0.8) in the solvent that forms, utilize and ultrasonicly make nano titanium oxide full and uniform dispersion wherein, subsequently by 10.0%(w/w) additive joins in dissolving tank, 32.0%(w/w is added after uniform stirring 15 min) cellulose acetate, fully stirs and leaves standstill and obtain casting solution 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; 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, deionized water is cleaned and is namely obtained cellulose acetate/nano titanium oxide 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 16.5L/m
2more than h, reverse flux salt is less than 3.5g/m
2h, surface contact angle is 60.2 °.
embodiment 2:
The ratio of nano titanium oxide, cellulose acetate is adjusted to 4.0%(w/w), 30.0%(w/w), remaining is with embodiment 1.The cellulose acetate obtained/nanometer titanium dioxide blending doughnut forward osmosis membrane 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 4.0g/m
2h, surface contact angle is 58.2 °.
embodiment 3:
The ratio of polyethylene glycol/lithium chloride compound additive is adjusted to 8.0%(w/w), 1-METHYLPYRROLIDONE and 1, the ratio of 4-dioxane mixed solvent is adjusted to 57.9%(w/w) (1-METHYLPYRROLIDONE: Isosorbide-5-Nitrae-dioxane=1:2.0), remaining is with embodiment 1.The cellulose acetate obtained/nanometer titanium dioxide blending doughnut forward osmosis membrane utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 15.6L/m
2more than h, reverse flux salt is less than 3.9g/m
2h, surface contact angle is 60.8 °.
embodiment 4:
Coagulation bath temperature is adjusted to 60 DEG C, remaining is with embodiment 1.The cellulose acetate obtained/nanometer titanium dioxide blending doughnut forward osmosis membrane utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 17.7L/m
2more than h, reverse flux salt is less than 4.1g/m
2h, surface contact angle is 59.6 °.
embodiment 5:
The ratio of cellulose acetate is adjusted to 26.0%(w/w), the ratio of mixed solvent is adjusted to 61.9%(w/w) (volume ratio of 1-METHYLPYRROLIDONE and Isosorbide-5-Nitrae-dioxane is adjusted to 1:1.5), remaining is with embodiment 1.The cellulose acetate obtained/nanometer titanium dioxide blending doughnut forward osmosis membrane utilizes 1M NaCl as driving liquid, deionized water as material liquid, and in the testing time of 1h, its pure water flux reaches 18.9L/m
2more than h, reverse flux salt is less than 4.5g/m
2h, surface contact angle is 59.7 °.
comparative example 1:
By 32%(W/W) cellulose acetate, 10.0%(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 cellulose acetate/nano titanium oxide 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 15.1L/m
2more than h, reverse flux salt is less than 6.5g/m
2h, surface contact angle is 65.2 °.
Claims (5)
1. cellulose acetate/nano titanium oxide mixed-matrix doughnut forward osmosis membrane, is characterized in that adopting following methods to make:
By 0.05% ~ 4.0%(w/w) nano titanium oxide, 0.01% ~ 1.0%(w/w) graphene oxide joins 1-METHYLPYRROLIDONE or dimethylacetylamide or dimethyl formamide and 1, in the solvent of 4-dioxane composition, utilize and ultrasonicly make nano titanium oxide full and uniform dispersion wherein, subsequently by 3.0 ~ 21.0%(w/w) additive joins in dissolving tank, 15.0% ~ 40.0%(w/w is added after uniform stirring 5 ~ 60min) cellulose acetate, fully stirs and leaves standstill and obtain casting solution at 20 ~ 70 DEG C of temperature; 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; Enter into the outer coagulating basin that 20 DEG C ~ 70 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, deionized water is cleaned and is namely obtained cellulose acetate/nano titanium oxide mixed-matrix doughnut forward osmosis membrane.
2. forward osmosis membrane according to claim 1, is characterized in that: described solvent N-methyl pyrilidone or dimethylacetylamide or dimethyl formamide: Isosorbide-5-Nitrae-dioxane=1:0.2 ~ 10.0.
3. forward osmosis membrane according to claim 1, is characterized in that: the temperature of described coagulating bath is 20 DEG C ~ 70 DEG C.
4. forward osmosis membrane according to claim 1, is characterized in that: described nano titanium oxide is that anatase titanium dioxide combines with rutile-type, and particle diameter is 20-50nm.
5. forward osmosis membrane according to claim 1, it is characterized in that: described forward osmosis membrane formula of casting: cellulose acetate 15.0% ~ 40.0%(w/w), pore-foaming agent 3.0 ~ 21.0%(w/w), nano titanium oxide 0.05% ~ 4.0%(w/w), Graphene 0.01% ~ 1.0%(w/w), dimethyl formamide or dimethylacetylamide or 1-METHYLPYRROLIDONE: Isosorbide-5-Nitrae-dioxane=1: 0.2 ~ 10.0.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771694A (en) * | 2016-05-06 | 2016-07-20 | 王泽陆 | Filtering membrane material applied to air purification and preparation method thereof |
| CN106492637A (en) * | 2016-12-14 | 2017-03-15 | 东华大学 | Positive osmosis composite membrane of a kind of TiO2/PSF nanofibers and preparation method thereof |
| 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 |
| CN109078630A (en) * | 2018-08-28 | 2018-12-25 | 山东圣泉新材料股份有限公司 | A kind of composite photo-catalyst and its preparation method and application |
| TWI664150B (en) * | 2018-05-30 | 2019-07-01 | National Taiwan University Of Science And Technology | Oil separation membrane and producing method thereof |
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2015
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771694A (en) * | 2016-05-06 | 2016-07-20 | 王泽陆 | Filtering membrane material applied to air purification and preparation method thereof |
| CN105771694B (en) * | 2016-05-06 | 2018-04-10 | 王梦梦 | A kind of filter membrane material for being applied to purification air and preparation method thereof |
| CN106492637A (en) * | 2016-12-14 | 2017-03-15 | 东华大学 | Positive osmosis composite membrane of a kind of TiO2/PSF nanofibers and preparation method thereof |
| 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 |
| TWI664150B (en) * | 2018-05-30 | 2019-07-01 | National Taiwan University Of Science And Technology | Oil separation membrane and producing method thereof |
| CN109078630A (en) * | 2018-08-28 | 2018-12-25 | 山东圣泉新材料股份有限公司 | A kind of composite photo-catalyst and its preparation method and application |
| CN109078630B (en) * | 2018-08-28 | 2021-10-08 | 山东圣泉新材料股份有限公司 | Composite photocatalyst and preparation method and application thereof |
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Application publication date: 20150916 |