CN105169971A - Reverse osmosis composite membrane - Google Patents
Reverse osmosis composite membrane Download PDFInfo
- Publication number
- CN105169971A CN105169971A CN201510571295.2A CN201510571295A CN105169971A CN 105169971 A CN105169971 A CN 105169971A CN 201510571295 A CN201510571295 A CN 201510571295A CN 105169971 A CN105169971 A CN 105169971A
- Authority
- CN
- China
- Prior art keywords
- reverse osmosis
- composite membrane
- osmosis composite
- organic phase
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention aims at providing a reverse osmosis composite membrane, which is prepared by adding ester-type co-solvent into organic-phase solvent for preparing a polyamide membrane. The co-solvent is added into an organic phase to carry out the interface polymerization, a two-phase mixing area can be formed, so that the interface polymerization process is affected. On the premise of not changing or increasing procedures for preparing the composite membrane in a conventional interface polymerization method, the polyamide reverse osmosis composite membrane with a high water flux can be prepared, the repeatability of the experiment is good, and the preparation cost is low. Compared with the existing method for adding inorganic nano particles, the co-solvent used in the co-solvent auxiliary method is a commercialized organic compound and is easy to obtain and low in cost; moreover, the co-solvent can be mixed with the organic phase, so that the problem that the inorganic nano particles are difficult to uniformly disperse in the solution can be avoided.
Description
Technical field
The invention belongs to interfacial polymerization and prepare reverse osmosis composite membrane technical field, be specifically related to a kind of reverse osmosis composite membrane.
Background technology
The freshwater resources of China account for 6% of global total amount, rank the 4th, the whole world.But water resource only has 2300m per capita
3, be only 1/4 of world average level, belong to one of country that water resource is the poorest per capita.The rapid growth of China's economy in recent years, be water for industrial use or the demand of domestic water all in quick increase, cause water resource growing tension.Therefore, the method for treating water such as desalinization, sewage purification becomes the strategic choice solving shortage of water resources gradually.
It is proposed by people such as the Reid of Univ Florida USA the earliest that reverse osmosis technology is applied to desalinization.Nineteen sixty Loeb and Sourirajan has made first asymmetric cellulose acetate reverse osmosis film (L-S).Twentieth century beginning of the seventies, the NS-100 composite membrane of Polaris company invention is the another milestone in film industry development process.1980, Filmtech company used toluenediamine and pyromellitic trimethylsilyl chloride to obtain FT-30 reverse osmosis composite membrane by interfacial polymerization, achieves the commercialization of composite membrane technology.Reverse osmosis composite membrane mainly adopts porous material (polysulfones, polyether sulfone or polyacrylonitrile etc.), and, as supporting layer, its thickness, at about 10 μm, is polymerized one deck ultra-thin parting absciss layer by interfacial polymerization on supporting layer top, and thickness is approximately 100nm.At present, reverse osmosis technology becomes the prevailing technology in desalination water market, the world today.
Current most widely used pressure-driven membrane material is PA membrane, and it has excellent filming performance and cost advantage; But, also there is the problems such as flux is not high, less stable in PA membrane.Prepare on the basis of polyamide reverse osmosis composite film at interfacial polymerization, researcher adopts multiple diverse ways to improve the water flux of film, to reach the object reducing and produce water cost.Zeolite molecular sieve is dispersed in (JournalofMembraneScience, 2007,294 (1): 1-7) in organic phase and improves the water flux of polyamide composite film by the people such as Hoek in 2007; CNT is added in organic phase and prepares polyamide active layer JournalofMembraneScience442 (2013) 18 – 26 to improve water flux by the people such as Shen in 2013.More than study is all prepare high performance film in solution by being added to by inorganic nanoparticles containing monomer, but inorganic nanoparticles can not be combined closely mutually with polymer in prepared aramid layer, invalid hole can be produced, inorganic nanoparticles is easily reunited in organic phase simultaneously, be difficult to disperse equably, also can affect film properties.And the preparation of nano particle has strict requirement, as needed nano particle to have certain particle diameter and aperture etc., preparation process is loaded down with trivial details and cost is higher.The difference of the nano particle performance of different batches can affect the repeatability of film.Therefore high flux, high rejection, the research of novel film materials of long-time steady operation can just seem particularly important.
Summary of the invention
The object of this invention is to provide a kind of reverse osmosis composite membrane, namely preparing polyamide reverse osmosis composite film by adding cosolvent in organic phase, thus the structure of active layer is changed, thus improve the performance of reverse osmosis composite membrane.
Applicant finds in long-term research, in the organic phase preparing PA membrane, be added into cosolvent, can effectively improve flux and rejection, thus facilitate the present invention.
First the present invention provides a kind of reverse osmosis composite membrane, is to prepare by being added into ester class cosolvent in the organic phase solvent preparing PA membrane.
Described ester class cosolvent general formula is (C
nh
2n+1)-COO-(CH
2)
n-CH
3, n≤0.
Preferred as embodiment, described ester class cosolvent is Ethyl formate;
As preferably, in described organic phase solvent, be dissolved with acid chloride groups (polynary acyl chlorides, polynary acyl chlorides is one or more in paraphthaloyl chloride, pyromellitic trimethylsilyl chloride (TMC) or m-phthaloyl chloride).
Described organic phase solvent is one or more in n-hexane, normal heptane, IsoparG, IsoparM, is preferably n-hexane.
The present invention also provides a kind of method preparing reverse osmosis composite membrane, specific as follows:
By generating one deck polyamide ultrathin separating layer containing amino aqueous phase solution and the organic phase solution generation interface polymerization reaction containing acid chloride groups on porous support layer, obtain reverse osmosis composite membrane; Add the ester class cosolvent separated that to dissolve each other with organic phase solution in the organic phase solution that wherein interfacial polymerization is used, its general formula is (C
nh
2n+1)-COO-(CH
2)
n-CH
3, n≤0.
In above-mentioned preparation method, porous support layer is polysulfones basement membrane or polyether sulfone basement membrane.
The present invention carries out interfacial polymerization by being joined in organic phase by cosolvent, can form two miscible districts, thus affect the process of interfacial polymerization.Consequently under not changing or increase conventional interface polymerization and preparing the prerequisite of composite membrane operation, the polyamide reverse osmosis composite film of high water flux can be obtained, and the favorable reproducibility of experiment, preparation cost is cheap.Compared with the method for existing interpolation inorganic nanoparticles, it is commercial organic compound that cosolvent spreads the cosolvent helping method to use, to be easy to get and cost is lower, and cosolvent and organic phase can be miscible, avoid inorganic nanoparticles and are difficult to homodisperse problem in the solution.
Accompanying drawing explanation
Fig. 1: reverse osmosis composite membrane prepared by the present invention is to the test of sodium chloride, Adlerika water flux and rejection.
Detailed description of the invention
Following embodiment is of the present invention further illustrating, instead of limits the scope of the invention.
The performance evaluation to reverse osmosis composite membrane adopted in description of the present invention adopts salt-stopping rate and water flux, system constant temperature 25 DEG C, preload pressure is 1.8MPa, and test pressure is 1.6MPa, the concentration of former water sodium chloride, magnesium sulfate is 2000ppm, and membrane area is 19.625cm
2.Salt-stopping rate is former water and the ratio producing water concentration; Water flux is the water volume of unit time by composite membrane, and unit is L/m
2h.
Embodiment 1
The aqueous solution of preparation containing 2%MPD, 0.15% lauryl sodium sulfate (SLS) is as aqueous phase, the hexane solution of the TMC of preparation 0.1% is as organic phase, polysulphone super-filter membrane is fixed in the clip of interfacial polymerization, pour on surface containing 2%MPD, the aqueous solution of 0.15% lauryl sodium sulfate, make it uniform spreading on PS membrane surface, after effect 2min, redundant solution outwelled and drain surface moisture to water stain-free, 0.1%TMC (in supersonic cleaning machine ultrasonic 1h) is slowly poured over film surface action 60s, 2min is dried in air after outwelling the organic phase solution of excess surface, finally be placed in baking oven heat treatment five minutes, the temperature of baking oven is set as 100 DEG C.The sodium chloride of reverse osmosis composite membrane test same concentrations prepared by the present embodiment and magnesium sulfate, salt-stopping rate is respectively: 99.47%, 99.63%; Water flux is respectively: 23.19L/m
2h, 24.04L/m
2h.
Embodiment 2
The Ethyl formate of 1% is added in the n-hexane containing 0.1%TMC, and replaces the organic phase in embodiment 1 with this.In addition, other all conditions are identical with embodiment 1.The sodium chloride of reverse osmosis composite membrane test same concentrations prepared by this method and magnesium sulfate, salt-stopping rate is respectively: 99.42%, 99.51%; Water flux is respectively: 28.19L/m
2h, 28.45L/m
2h, improves 21.56%, 18.34% respectively relative to embodiment 1.
Embodiment 3
The Ethyl formate of 2% is added in the n-hexane containing 0.1%TMC, and replaces the organic phase in embodiment 1 with this.In addition, other all conditions are identical with embodiment 1.The sodium chloride of reverse osmosis composite membrane test same concentrations prepared by this method and magnesium sulfate, salt-stopping rate is respectively: 95.63%, 98.34%; Water flux is respectively: 35.02L/m
2h, 34.13L/m
2h, improves 51.01%, 41.97% respectively relative to embodiment 1.
Embodiment 4
The Ethyl formate of 3% is added in the n-hexane containing 0.1%TMC, and replaces the organic phase in embodiment 1 with this.In addition, other all conditions are identical with embodiment 1.The sodium chloride of reverse osmosis composite membrane test same concentrations prepared by this method and magnesium sulfate, salt-stopping rate is respectively: 94.64%, 96.09%; Water flux is respectively: 38.28L/m
2h, 36.59L/m
2h, improves 65.07%, 52.2% respectively relative to embodiment 1.
Embodiment 5
The Ethyl formate of 4% is added in the n-hexane containing 0.1%TMC, and replaces the organic phase in embodiment 1 with this.In addition, other all conditions are identical with embodiment 1.The sodium chloride of reverse osmosis composite membrane test same concentrations prepared by this method and magnesium sulfate, salt-stopping rate is respectively: 90.87%, 93.54%; Water flux is respectively: 44.71L/m
2h, 41.33L/m
2h; 92.80%, 71.92% is improve respectively relative to embodiment 1.
Embodiment 6
The Ethyl formate of 5% is added in the n-hexane containing 0.1%TMC, and replaces the organic phase in embodiment 1 with this.In addition, other all conditions are identical with embodiment 1.The sodium chloride of reverse osmosis composite membrane test same concentrations prepared by this method and magnesium sulfate, salt-stopping rate is respectively: 59.29%, 78.93%; Water flux is respectively: 63.3L/m
2h, 62.21L/m
2h; 173%, 158.7% (Fig. 1) is improve respectively relative to embodiment 1.
Claims (10)
1. a reverse osmosis composite membrane, is characterized in that, described reverse osmosis composite membrane prepares by being added into ester class cosolvent in the organic phase solvent preparing PA membrane.
2. reverse osmosis composite membrane as claimed in claim 1, is characterized in that described ester class cosolvent general formula is (C
nh
2n+1)-COO-(CH
2)
n-CH
3, n≤0.
3. reverse osmosis composite membrane as claimed in claim 1 or 2, is characterized in that described ester class cosolvent is Ethyl formate.
4. reverse osmosis composite membrane as claimed in claim, is characterized in that described organic phase solvent is one or more in normal heptane, IsoparG, IsoparM.
5. reverse osmosis composite membrane as claimed in claim 1, is characterized in that described organic phase solvent is n-hexane.
6. the reverse osmosis composite membrane as described in claim 1,4 or 5, is characterized in that being dissolved with acid chloride groups in described organic phase solvent.
7. reverse osmosis composite membrane as claimed in claim 6, is characterized in that described acid chloride groups is one or more in paraphthaloyl chloride, pyromellitic trimethylsilyl chloride or m-phthaloyl chloride.
8. prepare a method for reverse osmosis composite membrane according to claim 1, it is characterized in that, described method comprises the steps:
By generating one deck polyamide ultrathin separating layer containing amino aqueous phase solution and the organic phase solution generation interface polymerization reaction containing acid chloride groups on porous support layer, obtain reverse osmosis composite membrane; Add the ester class cosolvent separated that to dissolve each other with organic phase solution in the organic phase solution that wherein interfacial polymerization is used, its general formula is (C
nh
2n+1)-COO-(CH
2)
n-CH
3, n≤0.
9. method as claimed in claim 8, it is characterized in that, described ester class cosolvent is Ethyl formate.
10. method as claimed in claim 8, it is characterized in that, described porous support layer is polysulfones basement membrane or polyether sulfone basement membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510571295.2A CN105169971A (en) | 2015-09-09 | 2015-09-09 | Reverse osmosis composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510571295.2A CN105169971A (en) | 2015-09-09 | 2015-09-09 | Reverse osmosis composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105169971A true CN105169971A (en) | 2015-12-23 |
Family
ID=54892685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510571295.2A Pending CN105169971A (en) | 2015-09-09 | 2015-09-09 | Reverse osmosis composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105169971A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106943902A (en) * | 2017-04-17 | 2017-07-14 | 中国海洋大学 | Ester modified polyamide reverse osmosis composite film of a kind of silicic acid and preparation method thereof |
| CN111282453A (en) * | 2020-02-20 | 2020-06-16 | 汕头市奥斯博环保材料制造有限公司 | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane |
| CN113351028A (en) * | 2020-03-05 | 2021-09-07 | 中国石油化工股份有限公司 | Composite reverse osmosis membrane and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4770777A (en) * | 1987-01-29 | 1988-09-13 | Parker Hannifin Corporation | Microporous asymmetric polyamide membranes |
| CN1158274A (en) * | 1995-07-05 | 1997-09-03 | 日东电工株式会社 | Highly permeable composite reverse osmosis membrane |
| US6280791B1 (en) * | 1997-04-11 | 2001-08-28 | Cuno, Inc. | Process of making a three-region reinforced microporous filtration membrane |
| CN101460237A (en) * | 2006-05-12 | 2009-06-17 | 陶氏环球技术公司 | Modified membrane |
| CN104437132A (en) * | 2010-02-16 | 2015-03-25 | 日东电工株式会社 | Composite separation membrane and separation membrane element using the same |
-
2015
- 2015-09-09 CN CN201510571295.2A patent/CN105169971A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4770777A (en) * | 1987-01-29 | 1988-09-13 | Parker Hannifin Corporation | Microporous asymmetric polyamide membranes |
| CN1158274A (en) * | 1995-07-05 | 1997-09-03 | 日东电工株式会社 | Highly permeable composite reverse osmosis membrane |
| US6280791B1 (en) * | 1997-04-11 | 2001-08-28 | Cuno, Inc. | Process of making a three-region reinforced microporous filtration membrane |
| CN101460237A (en) * | 2006-05-12 | 2009-06-17 | 陶氏环球技术公司 | Modified membrane |
| CN104437132A (en) * | 2010-02-16 | 2015-03-25 | 日东电工株式会社 | Composite separation membrane and separation membrane element using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106943902A (en) * | 2017-04-17 | 2017-07-14 | 中国海洋大学 | Ester modified polyamide reverse osmosis composite film of a kind of silicic acid and preparation method thereof |
| CN111282453A (en) * | 2020-02-20 | 2020-06-16 | 汕头市奥斯博环保材料制造有限公司 | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane |
| CN111282453B (en) * | 2020-02-20 | 2021-05-11 | 汕头市奥斯博环保材料制造有限公司 | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane |
| CN113351028A (en) * | 2020-03-05 | 2021-09-07 | 中国石油化工股份有限公司 | Composite reverse osmosis membrane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ang et al. | A facile and versatile strategy for fabricating thin-film nanocomposite membranes with polydopamine-piperazine nanoparticles generated in situ | |
| Shen et al. | Tris (2-aminoethyl) amine in-situ modified thin-film composite membranes for forward osmosis applications | |
| CN1272093C (en) | Method for preparing polyvinylidene fluoride flat plate microporous compound film | |
| Mubashir et al. | Effect of spinning conditions on the fabrication of cellulose acetate hollow fiber membrane for CO2 separation from N2 and CH4 | |
| CN101791522B (en) | Hybridized composite reverse osmosis membrane containing carbon nano tubes and preparation method thereof | |
| CN104209022A (en) | High-flux polyamide/ZIF-8 nanofiltration composite film and preparation method thereof | |
| Maab et al. | Polyazole hollow fiber membranes for direct contact membrane distillation | |
| CN104906966A (en) | Cellulose acetate/functionalized graphene mixed media hollow fiber positive osmotic membrane | |
| Hua et al. | Thin-film composite tri-bore hollow fiber (TFC TbHF) membranes for isopropanol dehydration by pervaporation | |
| Cheng et al. | Enhanced pervaporation performance of polyamide membrane with synergistic effect of porous nanofibrous support and trace graphene oxide lamellae | |
| CN102580562B (en) | Method for preparing polyvinylidene fluoride composite cellulose acetate forward osmosis membrane | |
| Tsai et al. | Preparation of polyamide/polyacrylonitrile composite hollow fiber membrane by synchronous procedure of spinning and interfacial polymerization | |
| CN105396471A (en) | Preparation method of high water flux reverse osmosis membrane | |
| CN105214502A (en) | A kind of Nano Silver/Graphene/polyvinyl alcohol mixing matrix membrane and preparation method thereof | |
| CN104174299A (en) | High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof | |
| CN105169971A (en) | Reverse osmosis composite membrane | |
| CN104923086A (en) | Semi-aromatic polyamide compound reverse osmosis membrane and preparation method thereof | |
| CN111001317B (en) | High-flux high-selectivity composite nanofiltration membrane and preparation method thereof | |
| CN110559888B (en) | Amphipathic graphene oxide modified ultrathin composite nanofiltration membrane as well as preparation method and application thereof | |
| Lessan et al. | Tailoring the hierarchical porous structure within polyethersulfone/cellulose nanosheets mixed matrix membrane to achieve efficient dye/salt mixture fractionation | |
| Yin et al. | Polyamide thin film nanocomposite with in-situ co-constructed COFs for organic solvent nanofiltration | |
| CN108031304B (en) | Flat plate type mixed matrix forward osmosis membrane based on metal organic framework MIL-101(Cr) and preparation method | |
| KR101729183B1 (en) | Thin-film composite membrane for pressure-retarded osmosis | |
| CN103831026A (en) | Production technology of composite macaroni fibre nano filter membrane with high rejection rate | |
| CN109304101B (en) | Zwitterionic high-strength pollution-resistant forward osmosis membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151223 |
|
| WD01 | Invention patent application deemed withdrawn after publication |