CN106902637A - High performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube - Google Patents

High performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube Download PDF

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Publication number
CN106902637A
CN106902637A CN201710095478.0A CN201710095478A CN106902637A CN 106902637 A CN106902637 A CN 106902637A CN 201710095478 A CN201710095478 A CN 201710095478A CN 106902637 A CN106902637 A CN 106902637A
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osmosis membrane
forward osmosis
carbon nano
nano tube
high performance
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王立国
王秀菊
刘思全
何芳
王仲鹏
许伟颖
周凯丽
侯凯
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University of Jinan
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University of Jinan
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002Forward osmosis or direct osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06Flat membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/08Polysaccharides
    • B01D71/12Cellulose derivatives
    • B01D71/14Esters of organic acids
    • B01D71/16Cellulose acetate

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a kind of high performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube, belong to technical field of membrane separation.By 0.05%~2.0%(w/w)Hydroxyl carbon nano tube be dispersed in 58.0%~88.95% by ultrasound(w/w)Mixed solvent in, then with 1.0%~9.0%(w/w)Polyvinylpyrrolidone or polyethylene glycol, 3.0%~11.0%(w/w)Lactic acid, 7.0%~20.0%(w/w)Cellulose acetate add three neck round bottom flask together, in a certain order, to being completely dissolved, 6~24h of standing and defoaming prepares forward osmosis membrane casting solution to 3~16h of stirring and dissolving at a temperature of 15~80 DEG C;5~60mins is heat-treated using phase inversion striking on backing material and in 60~90 DEG C of deionized waters, that is, the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube is obtained.By the use of 1M NaCl as driving liquid, deionized water as material liquid, in the testing time of 1h, its pure water flux reaches 36.0L/m to forward osmosis membrane of the invention2More than h, reverse flux salt is less than 2.5g/m2•h。

Description

High performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube
Technical field
It is more particularly to a kind of to be based on hydroxyl the present invention relates to flat forward osmosis membrane of a kind of macromolecule and preparation method thereof The high performance flat formula forward osmosis membrane and preparation method of carbon nano tube.
Background technology
The deficient and increasingly serious water pollution of water resource has turned into the bottleneck of restriction social progress and economic development, new water Source is developed and effluent sewage recycling also turns into global question of common concern.Because seawater resources extremely enrich on the earth, And the substantial amounts of effluent sewage of generation, desalinization and sewage recycling have turned into the strategic choice for solving water resources crisis.Many Sewage recycling technology in, membrane separation technique is one of best selection.It is born as this key issue is solved Low energy consumption, the positive infiltration technology of Water Sproading rate high are right into desalinization and the research emphasis and focus in sewage recycling field Solve the problems, such as that shortage of water resources has important strategic importance.
Positive infiltration (forward osmosis, FO) is the membrane separation technique that a kind of dependence film both sides osmotic pressure drives, positive day Benefit is taken seriously, and related theoretical and application study achieves larger progress, has been successfully applied to desalinization, at waste water The field such as reason, food medicine, the energy.At present, common forward osmosis membrane mainly has three cellulose acetate membrane, cellulose diacetate Film, polybenzimidazole membrane, polyamide composite film etc., degree of commercialization is not high to be mainly a lack of forward osmosis membrane of good performance and fits Suitable driving liquid, and forward osmosis membrane is the key point of whole positive process of osmosis.High performance forward osmosis membrane and its material character Structure with film is closely related, it is seen that the membrane material and forward osmosis membrane preparation method of function admirable are particularly important.Common just oozes Permeable membrane preparation method has interfacial polymerization, double selection tunics to prepare three kinds of method and nanofiltration membrane modifying.Interfacial polymerization is prepared just Concentration polarization is more serious in osmosis composite membrane;Double selection tunics effectively reduce interior concentration polarization, but preparation technology is complex; NF membrane Modified Membrane is relatively low to the rejection and water flux of monovalent salt;Accordingly, it would be desirable to develop new forward osmosis membrane preparation technology To improve the separating property of forward osmosis membrane.
Eighties of last century sixties, foreign countries have had begun to the research of positive infiltration technology, using existing reverse osmosis membrane or receive Filter membrane carries out the application study of positive infiltration, as a result proves that existing reverse osmosis membrane or NF membrane are difficult to use in positive process of osmosis, but The performance for also demonstrating forward osmosis membrane simultaneously is closely related with membrane material, membrane structure;Then, all multimembrane scientific workers start Basic research prepared by forward osmosis membrane.Result of study shows, by selecting suitable membrane material, film preparation technique, can prepare The forward osmosis membrane of function admirable.The research of the positive infiltration technology of China is started late, and the current country aligns the research of infiltration technology, nothing By being that film preparation or membrane process are studied, still in the exploratory stage.Some film researchers explore cellulose family and just permeate The preparation condition of film, have studied influence of the various factors to forward osmosis membrane performance, but it is excellent not yet to prepare commercially viable performance Good forward osmosis membrane;The preparation and application study of forward osmosis membrane still shoulder heavy responsibilities.Respectively early stage studying enlightenments we, profit Blending technology modified membrane is used, is expected to improve water flux, salt-stopping rate, mechanical performance and the anti-fouling performance of forward osmosis membrane.Hair Bright patent ZL201410770001.4,201510245514.8 and ZL201410769752.4,201510245504.4 are adopted respectively Flat and doughnut forward osmosis membrane is prepared with acetyl cellulose blend with nano titanium oxide and Graphene, it is prepared just to ooze The separating property and permeance property of permeable membrane have obtained raising by a relatively large margin;But by selecting suitable material, still can be to made The water flux of standby forward osmosis membrane is further improved, and satisfaction is commercially produced and application demand.
CNT is with sp2A kind of preferable One-dimensional Quantum material that covalent bond is constituted, with Young's modulus very high And tensile strength, while have excellent conduction, thermal conductivity, heat-resisting, corrosion resistance, various premium properties such as slight workability, It is expected for each Material Field;Applied as multi-walled carbon nano-tubes is based on the biocompatibility and big specific surface area of its height In the preparation of seperation film.There is scientific research personnel that modified CNT is added to the active layer of film to prepare milipore filter to carry Their hydrophily high;Also someone is prepared for reverse osmosis membrane by the way that modified CNT is embedded into top layer, leads to its water Substantially rising, and rejection are measured without decline by a relatively large margin, and improves the resistance tocrocking of film.Therefore, as will be modified CNT prepares forward osmosis membrane with acetyl cellulose blend, is also expected to while water flux high, salt-stopping rate is obtained, also make just Permeable membrane product has stain resistance, and this provides new thinking for the research and development and application of forward osmosis membrane material.
How while hydrophilic nmature is obtained, make forward osmosis membrane that there is resistance tocrocking again and keep the stabilization of water flux Property, this is the problem that film scientific worker is thinking and studying always in recent years.The present invention is hydroxyl using modified carbon nano-tube Carbon nano tube improves structure and permeance property, the research of separating property of forward osmosis membrane, both at home and abroad there is not yet document report.
The content of the invention
It is an object of the invention to provide a kind of high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube, the present invention Another purpose be to provide the preparation method of the flat forward osmosis membrane.
To achieve the above object, the technical scheme taken of the present invention is:
A kind of high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube, is by the material composition of following mass percent 's:Polymeric film material 7.0%~20.0%(w/w), pore-foaming agent --- pore-foaming agent A 1.0%~9.0%(w/w)With pore-foaming agent B 3.0%~11.0%(w/w), hydroxyl carbon nano tube 0.05%~2.0%(w/w), solvent 58.0%~88.95%(w/w);
Described polymeric film material be cellulose diacetate and Triafol T in one kind or two kinds, content be 7.0%~ 20.0%(w/w);
Described hydroxyl carbon nano tube is commercial goods product hydroxyl multi-walled carbon nano-tube, and hydroxyl rate is 1.0~7.0%, Content is 0.05%~2.0%(w/w);
Described pore-foaming agent is the mixture of pore-foaming agent A and pore-foaming agent B;Described pore-foaming agent A is polyvinylpyrrolidone and gathers One kind of ethylene glycol, content is 1.0%~9.0%(w/w);The pore-foaming agent B is lactic acid, and content is 3.0%~11.0%(w/w);
The solvent is the mixing of dimethylformamide or dimethylacetylamide or N- methyl pyrrolidones and 1,4- dioxane Solvent, its volume ratio is dimethylformamide or dimethylacetylamide or N- methyl pyrrolidones:1,4- dioxane=1: 0.1~6.0, content is 58.0%~88.95%(w/w).
A kind of preparation method of the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube, comprises the following steps:
(1)A certain amount of hydroxyl carbon nano tube is added in mixed solvent, is allowed to fully uniform wherein using ultrasound Dispersion, is added in three neck round bottom flask after the completion of dispersion, and adds a certain amount of pore-foaming agent, stirs;
(2)A certain amount of polymeric film material is added in three neck round bottom flask, at a temperature of 15~80 DEG C stirring and dissolving 3~ To being completely dissolved, the initial casting solution of the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube is configured within 16 hours; Then, the casting solution that will be obtained is static at a temperature of stirring and dissolving to be placed 6~24 hours, the bubble of remaining in removing casting solution;
(3)Supporting layer is laid in and is cleaned and on dry glass plate, is then poured on glass plate a certain amount of casting solution, used Flat Membrane scraper striking film forming;After the nascent state film that will be formed evaporates 2~60 seconds at room temperature, the constant temperature of 5~60 DEG C of immersion Solidification forming in coagulating bath water tank, film shaping automatically disengage glass plate, after taking the film out in deionized water at normal temperature immersion 12~ 48 hours, then it is heat-treated 5~60 minutes in 60~90 DEG C of deionized water, that is, obtains the height based on hydroxyl carbon nano tube The flat forward osmosis membrane of performance.
Described supporting layer is one kind of polyester screen, non-woven fabrics, cotton yarn filter cloth, filter paper and nylon cloth, and its aperture is 60 ~280 mesh;
Evaporation time under described nascent state film normal temperature, refers to that prepared flat forward osmosis membrane is completed after sky in knifing Residence time in gas, evaporation time is 2~60 seconds;
Described heat treatment temperature and time, refer to the deionization water temperature being heat-treated to prepared flat forward osmosis membrane Degree and process time, heat treatment temperature are 60~90 DEG C, and heat treatment time is 5~60 minutes;
Described coagulating bath is deionized water.
The invention provides a kind of high performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube, will Hydroxyl carbon nano tube prepares mixed-matrix forward osmosis membrane in being incorporated into polymer, and it is good to assign mixed-matrix forward osmosis membrane Permeance property, separating property and antifouling property, this is innovation of the invention.Test result shows that prepared just oozes The pure water flux of permeable membrane and reverse flux salt have very big improvement.
The present invention is compared with prior art, with following beneficial effect:
(1)High performance flat formula forward osmosis membrane and tradition prepared by hydroxyl carbon nano tube blending and modifying provided by the present invention Cellulose acetate forward osmotic membrane, the mixed-matrix forward osmosis membrane based on CNT compare, its pure water flux and reverse salt are logical Measure and be obviously improved.
(2)Hydroxyl carbon nano tube blending and modifying provided by the present invention prepares the side of high performance flat formula forward osmosis membrane Method, equipment used is simple, easily-controllable, film preparation process is simple, assigns prepared forward osmosis membrane good infiltration while film forming Performance, separating property and antifouling property, easily realize industrialization.
Specific embodiment:
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1:
By 0.5%(W/W)Hydroxyl carbon nano tube be added to 49.5%(W/W)Dimethylformamide and 25.0%(W/W)1,4- bis- The ring group of oxygen six into mixed solvent in, be allowed to fully dispersed wherein using ultrasound, three mouthfuls are added to after the completion of dispersion In round-bottomed flask, and add 5.0%(W/W)Polyvinylpyrrolidone and 7.0%(W/W)Lactic acid composition mixing pore-foaming agent, Stir.By 13.0%(W/W)Cellulose diacetate be added in three neck round bottom flask, the stirring and dissolving 8 at a temperature of 55 DEG C Hour, to being completely dissolved, is configured to the initial casting solution of the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube;So Afterwards, the casting solution that will be obtained is static at a temperature of stirring and dissolving to be placed 12 hours, the bubble of remaining in removing casting solution.By 180 Purpose polyester screen is laid in be cleaned and on dry glass plate, then pours on glass plate a certain amount of casting solution, with flat Plate film scraper striking film forming;After the nascent state film that will be formed evaporates 20 seconds at room temperature, the constant temperature solidification bath water of 30 DEG C of immersion Solidification forming in groove, film shaping automatically disengages glass plate, is soaked 24 hours in deionized water at normal temperature after taking the film out, Ran Hou It is heat-treated 15 minutes in 75 DEG C of deionized water, that is, obtains the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube. By the use of 1MNaCl as liquid is driven, deionized water is used as material liquid, in the testing time of 1h, the pure water of prepared forward osmosis membrane Flux reaches 36.0L/m2More than h, reverse flux salt is less than 2.5g/m2•h。
Embodiment 2:
The content of hydroxyl carbon nano tube, dimethylformamide is adjusted to 0.05% respectively(W/W)With 49.95%(W/W), remaining Same embodiment 1.Then the performance of the obtained high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube is:Utilize , used as liquid is driven, deionized water is used as material liquid, in the testing time of 1h, the pure water flux of prepared forward osmosis membrane for 1MNaCl Reach 26.0L/m2More than h, reverse flux salt is less than 4.0g/m2•h。
Embodiment 3:
The content of hydroxyl carbon nano tube, dimethylformamide is adjusted to 2.0% respectively(W/W)With 48.0%(W/W), remaining With embodiment 1.Then the performance of the obtained high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube is:Utilize , used as liquid is driven, deionized water is used as material liquid, in the testing time of 1h, the pure water flux of prepared forward osmosis membrane for 1MNaCl Reach 33.5L/m2More than h, reverse flux salt is less than 3.0g/m2•h。
Embodiment 4:
Mixing pore-foaming agent is constituted by 5.0%(W/W)Polyvinylpyrrolidone and 7.0%(W/W)Lactic acid be adjusted to 1.0%(W/ W)Polyvinylpyrrolidone and 11.0%(W/W)Lactic acid, remaining is with embodiment 1.It is then obtained to be received based on hydroxylating carbon The performance of the high performance flat formula forward osmosis membrane of mitron is:By the use of 1MNaCl as driving liquid, deionized water as material liquid, In the testing time of 1h, the pure water flux of prepared forward osmosis membrane reaches 28.0L/m2More than h, reverse flux salt is less than 3.5g/ m2•h。
Embodiment 5:
Mixing pore-foaming agent is constituted by 5.0%(W/W)Polyvinylpyrrolidone and 7.0%(W/W)Lactic acid be adjusted to 9.0%(W/ W)Polyvinylpyrrolidone and 3.0%(W/W)Lactic acid, remaining is with embodiment 1.It is then obtained to be received based on hydroxylating carbon The performance of the high performance flat formula forward osmosis membrane of mitron is:By the use of 1MNaCl as driving liquid, deionized water as material liquid, In the testing time of 1h, the pure water flux of prepared forward osmosis membrane reaches 30.5L/m2More than h, reverse flux salt is less than 4.0g/ m2•h。
Embodiment 6:
The polyvinylpyrrolidone mixed in pore-foaming agent is replaced by PEG-4000, remaining is with embodiment 1.It is then made The performance of the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube be:By the use of 1MNaCl as liquid is driven, go Used as material liquid, in the testing time of 1h, the pure water flux of prepared forward osmosis membrane reaches 40.5L/m to ionized water2More than h, Reverse flux salt is less than 4.0g/m2•h。
Embodiment 7:
Coagulation bath temperature is adjusted to 60 DEG C by 30 DEG C, remaining is with embodiment 1.It is then obtained based on hydroxyl carbon nano tube The performance of high performance flat formula forward osmosis membrane be:By the use of 1MNaCl as drive liquid, deionized water as material liquid, 1h's In testing time, the pure water flux of prepared forward osmosis membrane reaches 39.5L/m2More than h, reverse flux salt is less than 3.5g/m2•h。
Embodiment 8:
Heat treatment temperature is adjusted to 90 DEG C by 75 DEG C, remaining is with embodiment 1.It is then obtained based on hydroxyl carbon nano tube The performance of high performance flat formula forward osmosis membrane be:By the use of 1MNaCl as drive liquid, deionized water as material liquid, 1h's In testing time, the pure water flux of prepared forward osmosis membrane reaches 32.0L/m2More than h, reverse flux salt is less than 3.0g/m2•h。
Embodiment 9:
Heat treatment time was adjusted to 60 minutes by 15 minutes, remaining is with embodiment 1.It is then obtained to be received based on hydroxylating carbon The performance of the high performance flat formula forward osmosis membrane of mitron is:By the use of 1MNaCl as driving liquid, deionized water as material liquid, In the testing time of 1h, the pure water flux of prepared forward osmosis membrane reaches 33.5L/m2More than h, reverse flux salt is less than 2.5g/ m2•h。
Comparative example 1:
By 50.0%(W/W)Dimethylformamide and 25.0%(W/W)The mixed solvent of 1,4- dioxane composition is added to three mouthfuls In round-bottomed flask, it is subsequently adding by 5.0%(W/W)Polyvinylpyrrolidone and 7.0%(W/W)The mixing pore-foaming agent of lactic acid composition, Stir.By 13.0%(W/W)Cellulose diacetate be added in three neck round bottom flask, the stirring and dissolving 8 at a temperature of 55 DEG C Hour, to being completely dissolved, is configured to the initial casting solution of flat Cellulose acetate forward osmotic membrane;Then, the casting solution that will be obtained It is static at a temperature of stirring and dissolving to place 12 hours, the bubble of remaining in removing casting solution.The polyester screen of 180 mesh is laid in Clean and on dry glass plate, then pour on glass plate a certain amount of casting solution, with Flat Membrane scraper striking film forming;Will After the nascent state film for being formed evaporates 20 seconds at room temperature, solidification forming in the constant temperature coagulating bath water tank of 30 DEG C of immersion, film shaping Glass plate is automatically disengaged, is soaked in deionized water at normal temperature after taking the film out 24 hours, it is then hot in 75 DEG C of deionized water Treatment 15 minutes, that is, obtain flat Cellulose acetate forward osmotic membrane.By the use of 1MNaCl as liquid is driven, deionized water is used as original Feed liquid, in the testing time of 1h, the pure water flux of prepared forward osmosis membrane reaches 21.0L/m2More than h, reverse flux salt is small In 5.5g/m2•h。
Comparative example 2:
By 0.5%(W/W)CNT be added to 49.5%(W/W)Dimethylformamide and 25.0%(W/W)1,4- dioxane In the mixed solvent of composition, it is allowed to fully dispersed wherein using ultrasound, three mouthfuls of round bottoms is added to after the completion of dispersion and is burnt In bottle, and add 5.0%(W/W)Polyvinylpyrrolidone and 7.0%(W/W)Lactic acid composition mixing pore-foaming agent, stirring is equal It is even.By 13.0%(W/W)Cellulose diacetate be added in three neck round bottom flask, stirring and dissolving 8 hours is extremely at a temperature of 55 DEG C It is completely dissolved, is configured to the initial casting solution of the high performance flat formula forward osmosis membrane based on CNT;Then, the casting that will be obtained Film liquid is static at a temperature of stirring and dissolving to place 12 hours, the bubble of remaining in removing casting solution.The polyester screen of 180 mesh is put down Be layered on and clean and on dry glass plate, then pour on glass plate a certain amount of casting solution, with the striking of Flat Membrane scraper into Film;After the nascent state film that will be formed evaporates 20 seconds at room temperature, solidification forming, film in the constant temperature coagulating bath water tank of 30 DEG C of immersion Shaping automatically disengages glass plate, is soaked 24 hours in deionized water at normal temperature after taking the film out, then in 75 DEG C of deionized water Middle heat treatment 15 minutes, that is, obtain the high performance flat formula forward osmosis membrane based on CNT.By the use of 1MNaCl as driving liquid, Used as material liquid, in the testing time of 1h, the pure water flux of prepared forward osmosis membrane reaches 26.5L/m to deionized water2H with On, reverse flux salt is less than 5.0g/m2•h。

Claims (10)

1. a kind of high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube, it is characterised in that contain in its casting solution Hydroxyl carbon nano tube, and influence the structure and performance of forward osmosis membrane;Casting solution by following mass percent material composition:It is poly- Compound membrane material 7.0%~20.0%(w/w), pore-foaming agent --- pore-foaming agent A 1.0%~9.0%(w/w)With pore-foaming agent B 3.0%~ 11.0%(w/w), hydroxyl carbon nano tube 0.05%~2.0%(w/w), solvent 58.0%~88.95%(w/w).
2. the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube according to claim 1, its feature exists In:Described forward osmosis membrane is to do-wet method preparation using traditional phase inversion.
3. the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube according to claim 1, its feature exists In:Described hydroxyl carbon nano tube be hydroxyl multi-walled carbon nano-tube, hydroxyl rate be 1.0~7.0%, content be 0.05%~ 2.0%(w/w).
4. the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube according to claim 1, it is characterised in that: Described cellulose acetate is one kind or two kinds in cellulose diacetate and Triafol T.
5. the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube according to claim 1, it is characterised in that: Described pore-foaming agent is the mixture of pore-foaming agent A and pore-foaming agent B;Described pore-foaming agent A is polyvinylpyrrolidone and poly- second two One kind of alcohol, content is 1.0%~9.0%(w/w);The pore-foaming agent B is lactic acid, and content is 3.0%~11.0%(w/w).
6. the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube according to claim 1, it is characterised in that: The solvent is that dimethylformamide or dimethylacetylamide or N- methyl pyrrolidones are molten with the mixing of 1,4- dioxane Agent, its volume ratio is dimethylformamide or dimethylacetylamide or N- methyl pyrrolidones:1,4- dioxane=1:0.1~ 6.0, content is 58.0%~88.95%(w/w).
7. a kind of preparation method of the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube, it is characterised in that it is wrapped Include:
(1)A certain amount of hydroxyl carbon nano tube is added in mixed solvent, is allowed to fully uniform wherein using ultrasound Dispersion, is added in three neck round bottom flask after the completion of dispersion, and adds a certain amount of pore-foaming agent, stirs;
(2)A certain amount of polymeric film material is added in three neck round bottom flask, at a temperature of 15~80 DEG C stirring and dissolving 3~ To being completely dissolved, the initial casting solution of the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube is configured within 16 hours; Then, the casting solution that will be obtained is static at a temperature of stirring and dissolving to be placed 6~24 hours, the bubble of remaining in removing casting solution;
(3)Supporting layer is laid in and is cleaned and on dry glass plate, is then poured on glass plate a certain amount of casting solution, used Flat Membrane scraper striking film forming;After the nascent state film that will be formed evaporates 2~60 seconds at room temperature, the constant temperature of 5~60 DEG C of immersion Solidification forming in coagulating bath water tank, film shaping automatically disengage glass plate, after taking the film out in deionized water at normal temperature immersion 12~ 48 hours, then it is heat-treated 5~60 minutes in 60~90 DEG C of deionized water, that is, obtains the height based on hydroxyl carbon nano tube The flat forward osmosis membrane of performance.
8. the preparation method of the high performance flat formula forward osmosis membrane based on hydroxyl carbon nano tube according to claim 7, It is characterized in that:Described supporting layer is one kind of polyester screen, non-woven fabrics, cotton yarn filter cloth, filter paper and nylon cloth, and its aperture is 60~280 mesh;Described coagulating bath is deionized water.
9. the preparation method of the high performance flat formula forward osmosis membrane based on aminated carbon nano tube according to claim 7, It is characterized in that:Evaporation time under described nascent state film normal temperature is 2~60 seconds.
10. the preparation method of the high performance flat formula forward osmosis membrane based on aminated carbon nano tube according to claim 7, It is characterized in that:Described heat treatment temperature is 60~90 DEG C, and described heat treatment time is 5~60 minutes.
CN201710095478.0A 2017-02-22 2017-02-22 High performance flat formula forward osmosis membrane and preparation method based on hydroxyl carbon nano tube Pending CN106902637A (en)

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CN109012197A (en) * 2018-07-20 2018-12-18 常州大学 A kind of polyimide composite film and preparation method for infiltration evaporation processing Halite water

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