CN104001434B - A kind of forward osmosis membrane and preparation method thereof - Google Patents
A kind of forward osmosis membrane and preparation method thereof Download PDFInfo
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- CN104001434B CN104001434B CN201410261477.5A CN201410261477A CN104001434B CN 104001434 B CN104001434 B CN 104001434B CN 201410261477 A CN201410261477 A CN 201410261477A CN 104001434 B CN104001434 B CN 104001434B
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- osmosis membrane
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Abstract
The object of this invention is to provide a kind of forward osmosis membrane and preparation method thereof, namely just permeating interior concentration polarization to effectively reduce, providing a kind of is thin layer composite forward osmosis membrane of supporting layer and preparation method thereof based on screen cloth, thus compensate for the deficiencies in the prior art.Forward osmosis membrane of the present invention, wherein supporting layer is screen cloth, and cortex is the aramid layer of compound on screen cloth.The supporting layer structure that the present invention utilizes screen cloth good proposes a brand-new thin layer composite forward osmosis membrane concept, opens the new way of domestic and international high-performance forward osmosis membrane.In addition, the present invention completes interfacial polymerization operation in screen surface, and obtains the forward osmosis membrane that performance significantly improves, and this is also for the preparation of other new materials provides new approaches.
Description
Technical field
The invention belongs to technical field of membrane separation, be specifically related to a kind of forward osmosis membrane and preparation method thereof.
Background technology
Positive infiltration technology (FO) is a kind of new membrane isolation technics using the selective permeable pressure head through film both sides as driving force.Forward osmosis membrane technology is gathered around and is had wide practical use, and compared to traditional counter-infiltration, it has the following advantages: just permeating is a kind of spontaneous separation process, does not therefore need additionally to provide pressure, reduces energy consumption; Non-pressure drives process effectively can reduce fouling membrane simultaneously; In separation process, the rate of recovery of water is higher than reverse osmosis process, and does not have 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 being still subject to a lot of condition, 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 the forward osmosis membrane of specialty, while the salt-stopping rate that maintenance is high, reduce concentration polarization, improve water flux.
The forward osmosis membrane of current viable commercial product is mainly produced by HTI company of the U.S., has higher salt-stopping rate and water flux, but still there is comparatively serious interior concentration polarization phenomenon, cause the permeable pressure head of film both sides to decline to a great extent, water flux is declined.Interior concentration polarization has become the obstacle hindering 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, namely just permeating interior concentration polarization to effectively reduce, providing a kind of is thin layer composite forward osmosis membrane of supporting layer and preparation method thereof based on screen cloth, thus compensate for the deficiencies in the prior art.
Forward osmosis membrane of the present invention, wherein supporting layer is screen cloth, and cortex is the aramid layer of compound on screen cloth.
Forward osmosis membrane of the present invention, it is prepared by following method
1) aqueous phase solution and oil-phase solution is prepared; Solute wherein in aqueous phase solution is the long-chain macromolecule of micromolecular compound containing amido and/or amino-contained;
The solute of oil-phase solution is the small-molecule substance containing acyl chlorides, and solvent is n-hexane or Isopars (ISOPAR);
Micromolecular compound containing amido is one or more in bis-phenol, diethylenetriamine, triethylene tetramine, 2,5-bis-anilinesulfonic acid, 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 four formyl chloride etc. one or more, the concentration in oil-phase solution is 0.5-10g/L.
Also optionally additive is added in aqueous phase solution, 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) screen cloth is cleaned with solution, then by screen cloth dry for standby at low temperatures;
Wherein screen cloth be mesh diameter from several microns to hundreds of micron, thickness 100 microns within natural silk bolting cloth, metallic sieve and the synthetic fibers such as Fypro and the polyester fiber screen clothes such as copper wire, stainless steel wire, nickel foam, zirconia, aluminium oxide; Described solution can select one or more the alternately cleanings in absolute ethyl alcohol, isopropyl alcohol, deionized water.
3) by step 2) screen cloth after process is placed in aqueous phase upper surface, then slowly evenly adds oil phase at aqueous phase upper surface, leaves standstill reaction, after question response completes, product is taken out to immerse in deionized water to complete preparation.
The supporting layer structure that the present invention utilizes screen cloth good proposes a brand-new thin layer composite forward osmosis membrane concept, opens the new way of domestic and international high-performance forward osmosis membrane.In addition, the present invention completes interfacial polymerization operation in screen surface, and obtains 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
Use the sodium chloride solution of 1M as drawing liquid during prepared forward osmosis membrane test in following embodiment, deionized water is as material liquid.
Embodiment 1
1) prepare aqueous phase solution respectively, 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, 30 DEG C of oven dry after washed with de-ionized water.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in aqueous phase upper surface, slowly adds 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 that water flux is about 10L/m
2h, salt-stopping rate about 99.1%.
The performance for stability of test membrane is analyzed as follows: respectively film is immersed the HCl aqueous solution (pH=2), the NaOH aqueous solution (pH=12), NH
4hCO
3in solution 7 days, take out also clean with deionized water rinsing, then test its positive permeance property.Result shows, water flux respectively about 9.8,10.2 and 10.5L/m
2h, rejection respectively about 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 aqueous phase solution respectively, 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, 30 DEG C of oven dry after washed with de-ionized water.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in aqueous phase upper surface, slowly adds 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 that water flux is about 13L/m2h, salt-stopping rate about 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 aqueous phase solution respectively, 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, 30 DEG C of oven dry after washed with de-ionized water.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in aqueous phase upper surface, slowly adds 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 that water flux is about 15L/m
2h, salt-stopping rate about 99.5%.Visible, along with adding of polymine can improve water flux, 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 aqueous phase solution respectively, 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, 30 DEG C of oven dry after washed with de-ionized water.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in aqueous phase upper surface, slowly adds 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 that water flux is about 12L/m2h, salt-stopping rate about 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 aqueous phase solution respectively, 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, 30 DEG C of oven dry after washed with de-ionized water.
3) in beaker, add appropriate aqueous phase solution, screen cloth is placed in aqueous phase upper surface, slowly adds 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 that water flux is about 11.5L/m
2h, salt-stopping rate about 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 far away higher than the product film of HTI.Under identical testing conditions, the water flux of the film prepared by the present invention is far away higher than product film, and salt-stopping rate is lower slightly, but all more than 99%.
Claims (6)
1. a forward osmosis membrane, is characterized in that, the supporting layer of described forward osmosis membrane is screen cloth, and cortex is the aramid layer of compound on screen cloth, and its preparation method is as follows:
1) aqueous phase solution and oil-phase solution is prepared; Solute wherein in aqueous phase solution is the long-chain macromolecule of micromolecular compound containing amido and/or amino-contained; The solute of oil-phase solution is the small-molecule substance containing acyl chlorides, and solvent is n-hexane, Isopars;
2) screen cloth is cleaned with solution, then by screen cloth dry for standby at low temperatures;
3) by step 2) screen cloth after process is placed in aqueous phase upper surface, then slowly evenly adds oil phase at aqueous phase upper surface, leaves standstill reaction, after question response completes, product is taken out to immerse in deionized water to complete preparation.
2. forward osmosis membrane as claimed in claim 1, it is characterized in that, the described micromolecular compound containing amido is one or more in bis-phenol, diethylenetriamine, triethylene tetramine, 2,5-bis-anilinesulfonic acid, piperazine, o-phenylenediamine, m-phenylene diamine (MPD) and derivative thereof.
3. forward osmosis membrane as claimed in claim 1, 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.
4. forward osmosis membrane as claimed in claim 1, 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, all benzene four formyl chloride, and the concentration in oil-phase solution is 0.5-10g/L.
5. forward osmosis membrane as claimed in claim 1, it is characterized in that, also additive is added in described aqueous phase solution, comprise neopelex, lauryl sodium sulfate, polyethers, cyclic crown ether, tertiary amine, quaternary amine alkali, season phosphonium salt and hexadecyltrimethylammonium chloride, one or more in triethylamine, the concentration of additive in aqueous phase solution is 0-40g/L.
6. forward osmosis membrane as claimed in claim 1, it 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| CN105727768B (en) * | 2016-05-13 | 2018-07-10 | 高学理 | A kind of preparation method of the 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 |
| 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 |
| 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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| CN103170257A (en) * | 2013-03-21 | 2013-06-26 | 厦门大学 | Compound forward osmosis membrane and preparation method thereof |
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