CN104001434A - Forward osmosis membrane and preparation method thereof - Google Patents
Forward osmosis membrane and preparation method thereof Download PDFInfo
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- CN104001434A CN104001434A CN201410261477.5A CN201410261477A CN104001434A CN 104001434 A CN104001434 A CN 104001434A CN 201410261477 A CN201410261477 A CN 201410261477A CN 104001434 A CN104001434 A CN 104001434A
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- osmosis membrane
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Abstract
The invention provides a forward osmosis membrane and a preparation method of the forward osmosis membrane. The thin-layer composite forward osmosis membrane with a screen as a supporting layer and the preparation method of the forward osmosis membrane aim to effectively reduce forward osmosis and internal concentration polarization, thereby overcoming the defects in the prior art. According to the forward osmosis membrane, the supporting layer is the screen, and a skin layer is a polyamide layer compounded on the screen. By the adoption of the good supporting layer structure of the screen, the concept of the brand-new thin-layer composite forward osmosis membrane is put forward, and a new path of the forward osmosis membrane with high performance at home and abroad is opened up. In addition, the interfacial polymerization operation is conducted on the surface of the screen, the thin-layer forward osmosis membrane with the obviously improved performance is obtained; meanwhile, new ideas are provided for preparation of other new materials.
Description
Technical field
The invention belongs to membrane separation technique field, be specifically related to a kind of forward osmosis membrane and preparation method thereof.
Background technology
Positive infiltration technology (FO) is a kind of selectively to see through the permeable pressure head of film both sides as the new membrane isolation technics of driving force.Forward osmosis membrane technology is gathered around and is had wide practical use, and than traditional counter-infiltration, it has the following advantages: just permeating is a kind of spontaneous separation process, and therefore not needing additionally provides pressure, has reduced energy consumption; Non-pressure drives process can effectively reduce film pollution simultaneously; In separation process, the rate of recovery of water will be higher than reverse osmosis process, and there is no the discharge of dense water, belongs to eco-friendly new type water treatment technology.But as a kind of novel isolation technics, just permeating the restriction that is still subject to a lot of conditions, one of them lacks high performance forward osmosis membrane assembly exactly.Traditional reverse osmosis membrane can not directly apply in positive permeability and separation process, because its membrane structure can cause serious interior concentration polarization, finally causes extremely low water flux (well below desired value).Therefore must develop professional forward osmosis membrane, in the high salt-stopping rate of maintenance, reduce concentration polarization, improve water flux.
The commercial forward osmosis membrane of success is mainly to be produced by HTI company of the U.S. at present, has higher salt-stopping rate and water flux, but still has comparatively serious interior concentration polarization phenomenon, causes the permeable pressure head of film both sides to decline to a great extent, and water flux is declined.Interior concentration polarization has become an obstacle that hinders the development of forward osmosis membrane isolation technics.
Summary of the invention
The object of this invention is to provide a kind of forward osmosis membrane and preparation method thereof, just permeating interior concentration polarization for effective reduction, a kind of thin layer composite forward osmosis membrane that is supporting layer based on screen cloth and preparation method thereof is provided, thereby has made up the deficiencies in the prior art.
Forward osmosis membrane of the present invention, wherein supporting layer is screen cloth, cortex is aramid layer compound on screen cloth.
Forward osmosis membrane of the present invention, it is to prepare by following method
1) preparation aqueous phase solution and oil-phase solution; Wherein the solute in aqueous phase solution is the micromolecular compound that contains amido and/or the long-chain macromolecule of amino-contained;
The solute of oil-phase solution is the small-molecule substance containing acyl chlorides, and solvent is n-hexane or isoparaffin solvent (ISOPAR);
The micromolecular compound that contains amido is bis-phenol, diethylenetriamine, triethylene tetramine, 2, one or more in 5-bis-amido benzene sulfonic acids, piperazine, o-phenylenediamine, m-phenylene diamine (MPD) and derivative thereof;
The long-chain macromolecule of above-mentioned amino-contained/hydroxyl comprise polyvinyl alcohol, polymine, shitosan class, amination polyethylene glycol etc. one or more;
Containing the small-molecule substance of acyl chlorides, comprise m-phthaloyl chloride, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride, all benzene tetramethyl acyl chlorides etc. one or more, the concentration in oil-phase solution is 0.5-10g/L.
In aqueous phase solution, also optionally add additive, comprise neopelex, lauryl sodium sulfate, polyethers, cyclic crown ether, tertiary amine, quaternary amine alkali, season phosphonium salt and hexadecyltrimethylammonium chloride, triethylamine etc. one or more, the concentration in aqueous phase solution is 0-40g/L;
The solute of above-mentioned aqueous phase solution is preferably m-phenylene diamine (MPD), triethylamine and polymine, and mass ratio is 20:20:1.
2) clean screen cloth with solution, then by screen cloth dry for standby at low temperatures;
Wherein screen cloth be mesh diameter from several microns to 100 microns of hundreds of microns, thickness with interior natural silk bolting cloth, the synthetic fibers screen clothes such as the metallic sieves such as copper wire, stainless steel wire, nickel foam, zirconia, aluminium oxide and Fypro and polyester fiber; Described solution can be selected one or more the alternately cleanings in absolute ethyl alcohol, isopropyl alcohol, deionized water.
3) by step 2) screen cloth after treatment is placed in water upper surface, then slowly evenly adds oil phase at water upper surface, leaves standstill reaction, will product after question response completes take out to immerse in deionized water complete preparation.
The present invention utilizes the supporting layer structure that screen cloth is good to propose a brand-new thin layer composite forward osmosis membrane concept, the new way of having opened up domestic and international high-performance forward osmosis membrane.In addition, the present invention has completed interfacial polymerization operation in screen surface, and has obtained the forward osmosis membrane that performance significantly improves, and this is also for the preparation of other new materials provides new approaches.
Detailed description of the invention
When prepared forward osmosis membrane is tested in following embodiment, use the sodium chloride solution of 1M as drawing liquid, deionized water is as material liquid.
Embodiment 1
1) prepare respectively aqueous phase solution, solvent is deionized water, and solute is m-phenylene diamine (MPD) and triethylamine, and concentration is 20g/L; Oil-phase solution, solvent is n-hexane, and solvent is pyromellitic trimethylsilyl chloride, and concentration is 1g/L.
2) by 300 order polyester screen soaking and washing 30min in absolute ethyl alcohol, after washed with de-ionized water 30 DEG C of oven dry.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in to water upper surface, slowly add oil phase, leave standstill reaction 30min.After question response completes, product is taken out in immersion deionized water for subsequent use.
Forward osmosis membrane test result is the about 10L/m of water flux
2h, salt-stopping rate approximately 99.1%.
The performance for stability of test membrane is analyzed as follows: respectively film is immersed to the HCl aqueous solution (pH=2), the NaOH aqueous solution (pH=12), NH
4hCO
3in solution 7 days, take out and rinse well by deionized water, then test its positive permeance property.Result shows, water flux respectively approximately 9.8,10.2 and 10.5L/m
2h, rejection respectively approximately 99.2%, 99.1% and 99.3%.As can be seen here, this film shows good resistance to acids and bases and chemical stability.
Embodiment 2
1) prepare respectively aqueous phase solution, solvent is deionized water, and solute is m-phenylene diamine (MPD), triethylamine and polymine, and concentration is respectively 20g/L, 20g/L and 1g/L; Oil-phase solution, solvent is n-hexane, and solvent is pyromellitic trimethylsilyl chloride, and concentration is 1g/L.
2) by 300 order polyester screen soaking and washing 30min in absolute ethyl alcohol, after washed with de-ionized water 30 DEG C of oven dry.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in to water upper surface, slowly add oil phase, leave standstill reaction 30min.After question response completes, product is taken out in immersion deionized water for subsequent use.
Forward osmosis membrane test result is the about 13L/m2h of water flux, salt-stopping rate approximately 99.7%.
The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Embodiment 3.
1) prepare respectively aqueous phase solution, solvent is deionized water, and solute is m-phenylene diamine (MPD), triethylamine and polymine, and concentration is respectively 20g/L, 20g/L and 5g/L; Oil-phase solution, solvent is n-hexane, and solvent is pyromellitic trimethylsilyl chloride, and concentration is 1g/L.
2) by 300 order polyester screen soaking and washing 30min in absolute ethyl alcohol, after washed with de-ionized water 30 DEG C of oven dry.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in to water upper surface, slowly add oil phase, leave standstill reaction 30min.After question response completes, product is taken out in immersion deionized water for subsequent use.
Forward osmosis membrane test result is the about 15L/m of water flux
2h, salt-stopping rate approximately 99.5%.Visible, along with can improve water flux adding of polymine, and water flux increases along with the increase of polymine concentration.
The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Embodiment 4
1) prepare respectively aqueous phase solution, solvent is deionized water, and solute is m-phenylene diamine (MPD), triethylamine and polymine, and concentration is respectively 20g/L, 20g/L and 1g/L; Oil-phase solution, solvent is n-hexane, and solvent is pyromellitic trimethylsilyl chloride, and concentration is 1g/L.
2) by 500 order polyester screen soaking and washing 30min in absolute ethyl alcohol, after washed with de-ionized water 30 DEG C of oven dry.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in to water upper surface, slowly add oil phase, leave standstill reaction 30min.After question response completes, product is taken out in immersion deionized water for subsequent use.
Forward osmosis membrane test result is the about 12L/m2h of water flux, salt-stopping rate approximately 99.9%.
The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Embodiment 5.
1) prepare respectively aqueous phase solution, solvent is deionized water, and solute is m-phenylene diamine (MPD), triethylamine and polymine, and concentration is respectively 20g/L, 20g/L and 1g/L; Oil-phase solution, solvent is n-hexane, and solvent is pyromellitic trimethylsilyl chloride, and concentration is 1g/L.
2) by 800 order polyester screen soaking and washing 30min in absolute ethyl alcohol, after washed with de-ionized water 30 DEG C of oven dry.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in to water upper surface, slowly add oil phase, leave standstill reaction 30min.After question response completes, product is taken out in immersion deionized water for subsequent use.
Forward osmosis membrane test result is the about 11.5L/m of water flux
2h, salt-stopping rate approximately 99.6%.Visible, screen cloth mesh size has impact to water flux, and along with mesh reduces, water flux slightly reduces.
The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Reference examples 1.
The positive permeance property of the commercialization thin layer composite forward osmosis membrane of test HTI company, with 1M NaCl, as drawing liquid, deionized water is as material liquid.Under the existing tester condition of inventor, test result is as follows: water flux is 3L/m
2h, salt-stopping rate is 99.8%.
Result shows: the positive permeance property of novel high water flux thin layer composite forward osmosis membrane prepared by the present invention will be far away higher than the product film of HTI.Under identical test condition, the water flux of the prepared film of the present invention is far away higher than product film, and salt-stopping rate is lower slightly, but all more than 99%.
Claims (7)
1. a forward osmosis membrane, is characterized in that, the supporting layer of described forward osmosis membrane is screen cloth, and cortex is aramid layer compound on screen cloth.
2. forward osmosis membrane as claimed in claim 1, is characterized in that, a kind of preparation method of described forward osmosis membrane is as follows:
1) preparation aqueous phase solution and oil-phase solution; Wherein the solute in aqueous phase solution is the micromolecular compound that contains amido and/or the long-chain macromolecule of amino-contained; The solute of oil-phase solution is the small-molecule substance containing acyl chlorides, and solvent is n-hexane, isoparaffin solvent;
2) clean screen cloth with solution, then by screen cloth dry for standby at low temperatures;
3) by step 2) screen cloth after treatment is placed in water upper surface, then slowly evenly adds oil phase at water upper surface, leaves standstill reaction, will product after question response completes take out to immerse in deionized water complete preparation.
3. forward osmosis membrane as claimed in claim 2, it is characterized in that, the described micromolecular compound that contains amido is bis-phenol, diethylenetriamine, triethylene tetramine, 2, one or more in 5-bis-amido benzene sulfonic acids, piperazine, o-phenylenediamine, m-phenylene diamine (MPD) and derivative thereof.
4. forward osmosis membrane as claimed in claim 2, is characterized in that, the long-chain macromolecule of described amino-contained/hydroxyl is any one or several in polyvinyl alcohol, polymine, shitosan class, amination polyethylene glycol.
5. forward osmosis membrane as claimed in claim 2, it is characterized in that, the described small-molecule substance containing acyl chlorides is one or more in m-phthaloyl chloride, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride, equal benzene tetramethyl acyl chlorides, and the concentration in oil-phase solution is 0.5-10g/L.
6. forward osmosis membrane as claimed in claim 2, it is characterized in that, in described aqueous phase solution, also add additive, comprise neopelex, lauryl sodium sulfate, polyethers, cyclic crown ether, tertiary amine, quaternary amine alkali, season phosphonium salt and hexadecyltrimethylammonium chloride, triethylamine in one or more, the concentration of additive in aqueous phase solution is 0-40g/L.
7. forward osmosis membrane as claimed in claim 2, is characterized in that, the solute in described aqueous phase solution is m-phenylene diamine (MPD), triethylamine and polymine, and mass ratio is 20:20:1.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105126654A (en) * | 2015-09-30 | 2015-12-09 | 北京新源国能科技有限公司 | Hollow fiber forward osmosis membrane and preparing method thereof |
| CN105169972A (en) * | 2015-09-30 | 2015-12-23 | 北京新源国能科技有限公司 | Hollow fiber nanofiltration membrane and preparation method for producing hollow fiber nanofiltration membrane |
| CN105289322A (en) * | 2015-09-25 | 2016-02-03 | 天津工业大学 | Composite forward osmosis membrane based on superthin support layer and preparation method thereof |
| CN105727768A (en) * | 2016-05-13 | 2016-07-06 | 高学理 | Preparation method of self-supporting forward osmosis membrane based on chitosan |
| CN109647223A (en) * | 2018-11-14 | 2019-04-19 | 天津大学 | A kind of preparation method of the compound forward osmosis membrane in high activity site |
| CN110508154A (en) * | 2018-05-22 | 2019-11-29 | 中国石油化工股份有限公司 | Nanofiltration membrane and its preparation method and application |
| CN107913600B (en) * | 2017-09-29 | 2021-05-28 | 中国科学院重庆绿色智能技术研究院 | Composite forward osmosis membrane with proton exchange function and preparation method and application thereof |
| CN115779705A (en) * | 2022-12-27 | 2023-03-14 | 威海智洁环保技术有限公司 | Preparation method and application of polyamide/ceramic composite solvent-resistant nanofiltration membrane |
| CN115888430A (en) * | 2022-11-09 | 2023-04-04 | 江苏德环环保集团有限公司 | Graphene oxide/aminated attapulgite intercalation compound surface modified forward osmosis membrane and preparation method thereof |
| CN116043020A (en) * | 2022-12-28 | 2023-05-02 | 西安金藏膜环保科技有限公司 | Method for concentrating and recycling lithium cobalt manganese from waste batteries by using interlayer forward osmosis membrane |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289322A (en) * | 2015-09-25 | 2016-02-03 | 天津工业大学 | Composite forward osmosis membrane based on superthin support layer and preparation method thereof |
| CN105126654A (en) * | 2015-09-30 | 2015-12-09 | 北京新源国能科技有限公司 | Hollow fiber forward osmosis membrane and preparing method thereof |
| CN105169972A (en) * | 2015-09-30 | 2015-12-23 | 北京新源国能科技有限公司 | Hollow fiber nanofiltration membrane and preparation method for producing hollow fiber nanofiltration membrane |
| CN105727768A (en) * | 2016-05-13 | 2016-07-06 | 高学理 | Preparation method of self-supporting forward osmosis membrane based on chitosan |
| CN107913600B (en) * | 2017-09-29 | 2021-05-28 | 中国科学院重庆绿色智能技术研究院 | Composite forward osmosis membrane with proton exchange function and preparation method and application thereof |
| CN110508154A (en) * | 2018-05-22 | 2019-11-29 | 中国石油化工股份有限公司 | Nanofiltration membrane and its preparation method and application |
| CN109647223A (en) * | 2018-11-14 | 2019-04-19 | 天津大学 | A kind of preparation method of the compound forward osmosis membrane in high activity site |
| CN115888430A (en) * | 2022-11-09 | 2023-04-04 | 江苏德环环保集团有限公司 | Graphene oxide/aminated attapulgite intercalation compound surface modified forward osmosis membrane and preparation method thereof |
| CN115888430B (en) * | 2022-11-09 | 2023-11-14 | 江苏德环环保集团有限公司 | Graphene oxide/amination attapulgite intercalation compound surface modified forward osmosis membrane and preparation method thereof |
| CN115779705A (en) * | 2022-12-27 | 2023-03-14 | 威海智洁环保技术有限公司 | Preparation method and application of polyamide/ceramic composite solvent-resistant nanofiltration membrane |
| CN115779705B (en) * | 2022-12-27 | 2024-03-26 | 威海智洁环保技术有限公司 | Preparation method and application of polyamide/ceramic composite solvent-resistant nanofiltration membrane |
| CN116043020A (en) * | 2022-12-28 | 2023-05-02 | 西安金藏膜环保科技有限公司 | Method for concentrating and recycling lithium cobalt manganese from waste batteries by using interlayer forward osmosis membrane |
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