CN1954901A - Polyester amide reverse osmosis compound film and its preparation method - Google Patents
Polyester amide reverse osmosis compound film and its preparation method Download PDFInfo
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- CN1954901A CN1954901A CN 200510104327 CN200510104327A CN1954901A CN 1954901 A CN1954901 A CN 1954901A CN 200510104327 CN200510104327 CN 200510104327 CN 200510104327 A CN200510104327 A CN 200510104327A CN 1954901 A CN1954901 A CN 1954901A
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- reverse osmosis
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Abstract
A composite reverse osmosis polyester-amide membrane is composed of a porous supporting layer, and a compact polyester-amide surface layer prepared by interface polymerization between aminoglucose or aminobiglucose or the mixture of aminoglucose and metaphenyldiamine and the polyatomic acyl chloride. Its preparing process includes such steps as immersing the one surface of polysulfone film in the aqueous solution of amino monomer, dripdrying, interface polymerization reaction on the solution of polyatomic acyl chloride, drying, heat treating and rinsing in deionized water. It has high water throughput.
Description
Technical field
The present invention relates to a kind of reverse osmosis composite membrane and preparation method thereof, a kind of specifically Polyester amide reverse osmosis compound film and its preparation method.
Background technology
Counter-infiltration has purifying rate height, low cost and other advantages as one of state-of-the-art membrane separation technique in the world at present, is widely used in fields such as seawater and brackish water desalination, pure water and ultra-pure water preparation, water for industrial use processing, waste water reclaiming.Reverse osmosis membrane is the core of reverse osmosis technology.Nineteen sixty, the Loeb of California, USA university and Sourirajan etc. have made high desalination (98.6%), the high flux (259L/dm under the 10.1MPa that has historic significance in the world first
2) asymmetric acetate fiber reverse osmosis membrane, promoted the development of reverse osmosis membrane technology widely.1978, scholars such as U.S. J.E.Cadotte are obtaining important breakthrough aspect reverse osmosis composite membrane technology of preparing and the functional material research, researched and developed out first generation aromatic polyamides reverse osmosis composite membrane, compare with cellulose acetate, have advantages such as salt rejection rate height, flux is big, the operating pressure requirement is low.Reverse osmosis composite membrane is that ultra-thin functional cortical material is carried on the porous supporting body and forms through distinct methods.And membrane material and supporter can be selected respectively, thereby help realizing the film properties optimization.U.S. Filmtec company had released FT-30 high-performance reverse osmosis composite membrane in 1980, had realized the commercialization of reverse osmosis composite membrane technology, thereby made the reverse osmosis composite membrane technology obtain epoch-making progress.
Aromatic polyamide film salt rejection rate height, flux are big, and anti-biodegradation, and machinery, heat and chemical stability are good is one of two big topmost reverse osmosis membranes in the world at present, but its resistance to oxidation, contamination resistance are relatively poor.At present, employing is carried out the non-oxidizability that modification, development of new polymerization single polymerization monomer and polymerization technique improve the aromatic polyamide reverse osmosis composite membrane to face usually.The anti-pollution type low pressure reverse osmosis composite membrane LF10 series that the Nitto Denko company of Japan released in 1997 is exactly at traditional aromatic polyamide membrane surface recombination last layer PVA, has not only weakened the elecrtonegativity on film surface but also has improved the hydrophily and the chlorine resistance of film.But carrying out modification on face causes membrane flux to reduce easily.Usefulness polyamine such as Kim and polyhydric phenols mix and carry out the single face interfacial polymerization with polynary solution of acid chloride again, promptly introduce the ester function key in polyamide, and its chlorine-resistant property is improved greatly.But other performances such as salt rejection rate and water flux are unsatisfactory.
Summary of the invention
At the problems referred to above, the purpose of this invention is to provide a kind of high desalination rate, high flux, sludge proof polyester amide reverse osmosis compound film, and its preparation method is provided.
Polyester amide reverse osmosis compound film of the present invention comprises the supporting layer of one deck porous and the polyesteramide selective separating of one deck densification.
The supporting layer of described porous can be polysulfones, polyether sulfone, SPSF or sulfonated polyether sulfone;
Described polyesteramide selective separating is obtained by interfacial polymerization by the mixture and the polynary acyl chlorides of Glucosamine, amino glucobiose or Glucosamine and m-phenylene diamine (MPD);
The thickness of described polyesteramide selective separating is between 50～200nm.
The preparation method of polyester amide reverse osmosis compound film may further comprise the steps:
(1) polysulfones support membrane single face is immersed the aqueous solution of 2% amino monomers;
(2) treat that the surface drains after, carry out interface polymerization reaction with more than 0.1～0.2% yuan of solution of acid chloride;
(3) air drying 1～5 minute;
(4) 50～100 ℃ of heat treatment 3～10 minutes;
(5) rinsed with deionized water makes reverse osmosis composite membrane.
The reverse osmosis composite membrane performance test:
It in concentration the performance of test membrane under the condition of 25 ℃ of sodium-chloride water solution, operating pressure 1.6MPa, temperature of 20000mg/L.Salt rejection rate (R) and water flux (J) computing formula are respectively:
The specific embodiment
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1
2% (wt%) Glucosamine and 0.1% (wt%) lauryl sodium sulfate are made into aqueous phase solution, regulate pH=12 with NaOH; Pyromellitic trimethylsilyl chloride (TMC) is dissolved in is made into 0.1% (wt%) organic phase solution in the n-hexane.Make in the aqueous phase solution of polysulfones support membrane single face immersion 2% 3 minutes time; Drop removes superfluous water solution, reacts 30 seconds with organic facies; Drop goes organic facies, and air drying 1 minute; In air dry oven in 75 ℃ of heat treatments 3 minutes; Rinsed with deionized water makes reverse osmosis composite membrane.
With the reverse osmosis composite membrane drying that makes above, survey its INFRARED ABSORPTION with the attenuate total reflection Fourier infrared spectrograph.Found that: 1663cm
-1, 1540cm
-1There is absorption at the place, is respectively acid amides I band and acid amides II band characteristic peak characteristic peak, has proved the generation of amido link.1013cm
-1The C of place
6The absworption peak of hydroxyl disappears, simultaneously at 1540cm
-1The absworption peak of ester group C-O-C occurs, proved the generation of ester group.
Embodiment 2
According to the step identical with embodiment 1, the preparation reverse osmosis composite membrane.Water consists of: 1.2% (wt%) m-phenylene diamine (MPD), 0.8% (wt%) Glucosamine and 0.1% (wt%) lauryl sodium sulfate, regulate pH=12 with NaOH; Organic facies is that the TMC of 0.1% (wt%) is dissolved in the n-hexane and is made into; Make polysulfones support membrane single face immerse in the aqueous phase solution 3 minutes time; Drop removes superfluous water solution, reacts 60 seconds with organic facies; Drop goes organic facies, and air drying 3 minutes; In air dry oven in 85 ℃ of heat treatments 5 minutes; Rinsed with deionized water makes reverse osmosis composite membrane.
According to foregoing method, measure its performance.In concentration is that flux is 29.3L/m under 25 ℃ of sodium-chloride water solution, operating pressure 1.6MPa, the temperature of 20000mg/L
2H, salt rejection rate is 98.0.
Embodiment 3
According to the step identical with embodiment 1, the preparation reverse osmosis composite membrane.Water consists of: 1.2% (wt%) m-phenylene diamine (MPD), 0.8% (wt%) Glucosamine and 0.1% (wt%) lauryl sodium sulfate, regulate pH=12 with NaOH; Organic facies is that the TMC of 0.2% (wt%) is dissolved in C
12Be made in the solvent naphtha; Make polysulfones support membrane single face immerse in the aqueous phase solution 3 minutes time; Drop removes superfluous water solution, reacts 60 seconds with organic facies; Drop goes organic facies, and air drying 5 minutes; In air dry oven in 85 ℃ of heat treatments 10 minutes; Rinsed with deionized water makes reverse osmosis composite membrane.
According to foregoing method, measure its performance.In concentration is that flux is 20.9L/m under 25 ℃ of sodium-chloride water solution, operating pressure 1.6MPa, the temperature of 20000mg/L
2H, salt rejection rate is 98.6.
Comparative Examples 1
According to the step identical with embodiment 1, the preparation reverse osmosis composite membrane.Earlier 2% (wt%) triethylamine is dissolved in the deionized water, regulates pH=8 with hydrochloric acid; Again 2% (wt%) m-phenylene diamine (MPD) and 0.1% (wt%) lauryl sodium sulfate are dissolved in and wherein are made into water; Organic facies is that the TMC of 0.2% (wt%) is dissolved in C
12Be made in the solvent naphtha; Make polysulfones support membrane single face immerse in the aqueous phase solution 3 minutes time; Drop removes superfluous water solution, reacts 30 seconds with organic facies; Drop goes organic facies, and air drying 1 minute; In air dry oven in 75 ℃ of heat treatments 10 minutes; Rinsed with deionized water makes reverse osmosis composite membrane.
According to foregoing method, measure its performance.In concentration is that flux is 15.4L/m under 25 ℃ of sodium-chloride water solution, operating pressure 1.6MPa, the temperature of 20000mg/L
2H, salt rejection rate is 98.1.
Embodiment 4
The reverse osmosis composite membrane that embodiment 3 and Comparative Examples 1 is prepared soaked 5 hours in the liquor natrii hypochloritis who contains 1000ppm effective chlorine, took out, and spent ion-cleaning.In concentration is under 25 ℃ of sodium-chloride water solution, operating pressure 1.6MPa, the temperature of 20000mg/L, measures its flux and salt rejection rate.
The result is as shown in table 1:
The oxidative resistance experimental result of table 1 reverse osmosis composite membrane
| The film sequence number | Initial performance | Performance after the 5000ppmh clorox is handled | ||
| R(％) | J(L/m 2·h) | R(％) | J(L/m 2·h) | |
| Embodiment 3 | 98.6 | 20.9 | 97.6 | 23.2 |
| Comparative Examples 1 | 98.1 | 15.4 | 93.7 | 27.9 |
As can be seen, under the situation that has high desalination rate (＞98%) equally, polyester amide reverse osmosis compound film has higher water flux than aromatic polyamides reverse osmosis composite membrane from above-mentioned experimental result; And the oxidisability of anti-chlorine is also better.
Claims (5)
1. a polyester amide reverse osmosis compound film is characterized in that it comprises the supporting layer of one deck porous and the polyesteramide selective separating of one deck densification.
2. reverse osmosis composite membrane according to claim 1 is characterized in that described porous support layer can be polysulfones, polyether sulfone, SPSF or sulfonated polyether sulfone.
3. reverse osmosis composite membrane according to claim 1 is characterized in that described polyesteramide selective separating is obtained by interfacial polymerization by the mixture and the polynary acyl chlorides of Glucosamine, amino glucobiose or Glucosamine and m-phenylene diamine (MPD).
4. according to claim 1 or 3 described reverse osmosis composite membranes, the thickness that it is characterized in that described polyesteramide selective separating is between 50～200nm.
5. according to the preparation method of right 1 described polyester amide reverse osmosis compound film, may further comprise the steps:
(1) polysulfones support membrane single face is immersed the aqueous solution of 2% amino monomers;
(2) treat that the surface drains after, carry out interface polymerization reaction with more than 0.1～0.2% yuan of solution of acid chloride;
(3) air drying 1～5 minute;
(4) 50～100 ℃ of heat treatment 3～10 minutes;
(5) rinsed with deionized water makes reverse osmosis composite membrane.
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| CNB2005101043274A CN100484615C (en) | 2005-10-24 | 2005-10-24 | Polyester amide reverse osmosis compound film and its preparation method |
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| CNB2005101043274A CN100484615C (en) | 2005-10-24 | 2005-10-24 | Polyester amide reverse osmosis compound film and its preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940883A (en) * | 2010-08-03 | 2011-01-12 | 浙江大学 | Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves |
| CN102258948A (en) * | 2011-05-31 | 2011-11-30 | 南京帝膜净水材料开发有限公司 | Method for preparing polyamide reverse osmosis compound membrane |
| CN102527265A (en) * | 2010-12-15 | 2012-07-04 | 华东理工大学 | Membrane functional monomer containing hexafluoroisopropanol group and nanofiltration membrane preparation method thereof |
| CN103331110A (en) * | 2013-05-27 | 2013-10-02 | 天津工业大学 | Pollution-resistant chlorine polyamide-resistant reverse osmosis composite membrane and preparation method thereof |
| CN105032201A (en) * | 2009-08-24 | 2015-11-11 | Oasys水有限公司 | Forward osmosis membranes |
| CN111788251A (en) * | 2018-06-15 | 2020-10-16 | 株式会社Lg化学 | Composition for interfacial polymerization of polyamide and method for manufacturing water treatment separation membrane by using the same |
| CN115228300A (en) * | 2022-06-24 | 2022-10-25 | 河北工业大学 | Ion-selective nanofiltration membrane and preparation method and application thereof |
-
2005
- 2005-10-24 CN CNB2005101043274A patent/CN100484615C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032201A (en) * | 2009-08-24 | 2015-11-11 | Oasys水有限公司 | Forward osmosis membranes |
| CN105032201B (en) * | 2009-08-24 | 2018-08-14 | Oasys水有限公司 | Forward osmosis membranes |
| CN101940883A (en) * | 2010-08-03 | 2011-01-12 | 浙江大学 | Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves |
| CN102527265A (en) * | 2010-12-15 | 2012-07-04 | 华东理工大学 | Membrane functional monomer containing hexafluoroisopropanol group and nanofiltration membrane preparation method thereof |
| CN102527265B (en) * | 2010-12-15 | 2013-11-27 | 华东理工大学 | Membrane functional monomer containing hexafluoroisopropanol group and nanofiltration membrane preparation method thereof |
| CN102258948A (en) * | 2011-05-31 | 2011-11-30 | 南京帝膜净水材料开发有限公司 | Method for preparing polyamide reverse osmosis compound membrane |
| CN103331110A (en) * | 2013-05-27 | 2013-10-02 | 天津工业大学 | Pollution-resistant chlorine polyamide-resistant reverse osmosis composite membrane and preparation method thereof |
| CN103331110B (en) * | 2013-05-27 | 2015-03-04 | 天津工业大学 | Pollution-resistant chlorine polyamide-resistant reverse osmosis composite membrane and preparation method thereof |
| CN111788251A (en) * | 2018-06-15 | 2020-10-16 | 株式会社Lg化学 | Composition for interfacial polymerization of polyamide and method for manufacturing water treatment separation membrane by using the same |
| CN111788251B (en) * | 2018-06-15 | 2023-03-28 | 株式会社Lg化学 | Composition for interfacial polymerization of polyamide and method for manufacturing water treatment separation membrane by using the same |
| CN115228300A (en) * | 2022-06-24 | 2022-10-25 | 河北工业大学 | Ion-selective nanofiltration membrane and preparation method and application thereof |
| CN115228300B (en) * | 2022-06-24 | 2024-02-23 | 河北工业大学 | Ion-selective nanofiltration membrane and preparation method and application thereof |
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| CN100484615C (en) | 2009-05-06 |
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Assignee: Qingdao Hainuo Water-Supply Engineering Co., Ltd. Assignor: Ocean University of China Contract fulfillment period: 2009.5.6 to 2015.1.15 contract change Contract record no.: 2009370000194 Denomination of invention: Polyester amide reverse osmosis compound film and its preparation method Granted publication date: 20090506 License type: Exclusive license Record date: 2009.8.3 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.5.6 TO 2015.1.15; CHANGE OF CONTRACT Name of requester: QINGDAO HEINUO WATER UTILITY TECHNOLOGY CO., LTD. Effective date: 20090803 |
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