CN102941019A - Method for improving anti-pollution performance of reverse osmosis membrane element - Google Patents
Method for improving anti-pollution performance of reverse osmosis membrane element Download PDFInfo
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- CN102941019A CN102941019A CN2012105140201A CN201210514020A CN102941019A CN 102941019 A CN102941019 A CN 102941019A CN 2012105140201 A CN2012105140201 A CN 2012105140201A CN 201210514020 A CN201210514020 A CN 201210514020A CN 102941019 A CN102941019 A CN 102941019A
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- concentrated stream
- road net
- membrane element
- osmosis membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 51
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 12
- 230000003373 anti-fouling effect Effects 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000010148 water-pollination Effects 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 26
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000008859 change Effects 0.000 description 37
- 238000010612 desalination reaction Methods 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 16
- 238000012545 processing Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 239000003513 alkali Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010301 surface-oxidation reaction Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 102000014171 Milk Proteins Human genes 0.000 description 2
- 108010011756 Milk Proteins Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 235000021239 milk protein Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for improving the anti-pollution performance of a reverse osmosis membrane element. The method is characterized in that strong oxidization treatment is performed on the surface of a concentrated water passageway net in the membrane element by a strong oxidant with the concentration of 0.5-8mol/L, and the treated concentrated water passageway net is used for preparing an LP4040 membrane element. The method mainly comprises the following steps of: (1) preparing a treatment solution, namely preparing a concentrated sulfuric acid solution with the concentration of 0.5-8mol/L; (2) adding potassium dichromate according to the mass ratio of potassium dichromate to sulfuric acid being 1:30; (3) keeping the temperature of the treatment solution at 40 to 90 DEG C, and immersing the concentrated water passageway net into the treatment solution for 0.5 to 24 hours; and (4) taking out the concentrated water passageway net, washing with water, and drying the concentrated water passageway net in the air or with hot air. By the method, the concentrated water passageway net is subjected to oxidization treatment, so that the anti-pollution performance of the reverse osmosis membrane element can be effectively improved; the salt removing rate and the stability of membrane flux can be improved; and the service life of the reverse osmosis membrane element is prolonged.
Description
Technical field
The present invention relates to a kind of method that improves the reverse-osmosis membrane element antifouling property.
Background technology
In the use procedure of reverse osmosis membrane, because the existence of the trapped substances such as Suspended Matter in Water, inorganic matter, organic matter, microorganism is seeing through liquid through in the film body, trapped substance must produce progressive pollution to film body.Excessive film pollutes film properties is descended, even the due separation function of forfeiture film system.Usually, prevent that the method that membrane component pollutes from comprising: former water is carried out preliminary treatment, reduce suspension and content of organics in the water; Regulate water inlet pH value, keep the stability of water, prevent from forming on the face dirt; Film is carried out periodic cleaning; Carry out the stoppage in transit Protection when inactive; Regularly membrane component is changed.In addition, can also carry out certain processing to the concentrated stream road net in the membrane component, to improve the resistant to pollution performance of membrane component, the assurance reverse osmosis membrane system can be worked continually and steadily.
When separation, condensing protein or other large molecule solutes, " gel layer " is very large on the impact of film permeability rate.When certain and concentration polarization was not obvious when flow velocity, near linear increased the film permeability rate with the increase of pressure.After concentration polarization was worked, because pressure increases, permeability rate improved, and concentration polarization is thereupon serious, and permeability rate is improved and curved increase with pressure.After pressure was elevated to certain numerical value, when concentration polarization made film surface solute concentration reach capacity concentration, solute was separated out on the film surface, forms " gel layer "." gel layer " resistance plays a decisive role to the permeability rate of film at this moment, and permeability rate depends on pressure hardly.Therefore, to solute concentration one regularly, should manage to avoid to form " gel layer ", to obtain the best film permeability rate.
Chinese patent ZL200610024540.9 discloses a kind of preparation method of high-flux reverse osmosis membrane element, be before or after the reverse osmosis membrane diaphragm rolls step by step, oxidant with the different volumes concentration ratio carries out oxidation to the reverse osmosis membrane diaphragm, makes reverse-osmosis membrane element compared with prior art have higher product discharge.The method is carried out oxidation processes to the reverse osmosis membrane diaphragm in the membrane component, can improve water flux to a certain extent, but can not reduce the formation of " gel layer ", is unfavorable for the durable wear-resistant of diaphragm.
Summary of the invention
The invention provides a kind of method that improves the reverse-osmosis membrane element antifouling property, solved the problem of membrane component antifouling property deficiency in the prior art.
Technical scheme of the present invention is as described below.
A kind of method that improves the reverse-osmosis membrane element antifouling property is to utilize the oxidation means that the concentrated stream road net of reverse-osmosis membrane element is processed, and strengthens concentrated stream road net hydrophily and reduces it to the adsorption capacity of pollutant.
The method of above-mentioned raising reverse-osmosis membrane element antifouling property mainly may further comprise the steps:
(1) preparation of Treatment Solution: the concentrated sulfuric acid solution of preparation 0.5～8mol/L;
(2) mass ratio by potassium bichromate and sulfuric acid is that 1:30 adds potassium bichromate;
(3) temperature of keeping treatment fluid is put into treatment fluid with concentrated stream road net and is soaked 0.5～24h at 40～90 ℃;
(4) take out concentrated stream road net water and rinse well, then concentrated stream road net thickness is dried or air-dry with hot blast.
Concentrated stream road net thickness 1～100mil in the described step (3).
Concentrated stream road net in the described step (3) is by any or several composition the in polyethylene, polypropylene, polyacrylamide, polymethyl methacrylate, nylon and the polyurethane.
Beneficial effect of the present invention: concentrated stream road net is carried out strong oxidation processes, but the resistant to pollution performance of Effective Raise reverse-osmosis membrane element improves the stability of salt rejection rate and membrane flux, is conducive to prolong the life-span of reverse osmosis membrane diaphragm.
Description of drawings
Fig. 1 is for adopting the membrane module desalination rate of change figure after embodiment 1 processes concentrated stream road net;
Fig. 2 is for adopting the membrane module desalination rate of change figure after embodiment 2 processes concentrated stream road net;
Fig. 3 is that concentrated stream road net is without the membrane module desalination rate of change figure of any processing;
Fig. 4 is that concentrated stream road net is without the membrane module desalination rate of change figure of any processing;
Fig. 5 is for adopting the membrane module membrane flux rate of change figure after embodiment 1 processes concentrated stream road net;
Fig. 6 is for adopting the membrane module membrane flux rate of change figure after embodiment 2 processes concentrated stream road net;
Fig. 7 is that concentrated stream road net is without the membrane module membrane flux rate of change figure of any processing;
Fig. 8 is that concentrated stream road net is without the membrane module membrane flux rate of change figure of any processing;
Among the figure: A is the desalination rate of change behind the pollution 2h, and B is the desalination rate of change behind the alkali cleaning 1h; C is the desalination rate of change behind the Re-pollution 2h; D is again the desalination rate of change behind the alkali cleaning 1h; E is the membrane flux rate of change behind the pollution 2h, and F is the membrane flux rate of change behind the alkali cleaning 1h; G is the membrane flux rate of change behind the Re-pollution 2h; H is again the membrane flux rate of change behind the alkali cleaning 1h.
The specific embodiment
In order to deepen that the present invention is understood, the present invention is described in further detail below in conjunction with embodiment, and this embodiment only is used for explaining the present invention, does not consist of the restriction to protection domain of the present invention.
Embodiment 1
The concentrated sulfuric acid solution of preparation 200L 8mol/L is that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid, behind the dissolve complete solution is warming up to 70 ℃.Get and be of a size of 30000mm * 1067mm, thickness is that the polypropylene material concentrated stream road net of 27mil places 70 ℃ potassium bichromate sulfuric acid solution to carry out surface oxidation treatment, takes out behind the immersion 2h and fully takes out residual potassium bichromate sulfuric acid solution with washed with de-ionized water.Concentrated stream road net after cleaning adopts 60 ℃ of hot blasts air-dry.Concentrated stream road net after air-dry is rolled into the membrane module that specification is LP4040 and carries out follow-up performance and the contamination resistance evaluation with the counter-infiltration diaphragm.
Embodiment 2
The concentrated sulfuric acid solution of preparation 200L 3mol/L is that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid, behind the dissolve complete solution is warming up to 70 ℃.Get and be of a size of 30000mm * 1067mm, thickness is that the polypropylene material concentrated stream road net of 27mil places 70 ℃ potassium bichromate sulfuric acid solution to carry out surface oxidation treatment, takes out behind the immersion 10h and fully takes out residual potassium bichromate sulfuric acid solution with washed with de-ionized water.Concentrated stream road net after cleaning adopts 60 ℃ of hot blasts air-dry.Concentrated stream road net after air-dry is rolled into the membrane module that specification is LP4040 and carries out follow-up performance and the contamination resistance evaluation with the counter-infiltration diaphragm.
Embodiment 3
The concentrated sulfuric acid solution of preparation 200L 6mol/L is that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid, behind the dissolve complete solution is warming up to 90 ℃.Get and be of a size of 30000mm * 1067mm, thickness is that the polyacrylamide material concentrated stream road net of 100mil places 90 ℃ potassium bichromate sulfuric acid solution to carry out surface oxidation treatment, takes out behind the immersion 24h and fully takes out residual potassium bichromate sulfuric acid solution with washed with de-ionized water.Concentrated stream road net after cleaning dries.
Embodiment 4
The concentrated sulfuric acid solution of preparation 200L 6mol/L is that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid, behind the dissolve complete solution is warming up to 50 ℃.Get and be of a size of 30000mm * 1067mm, thickness is that the polyethylene material concentrated stream road net of 70mil places 50 ℃ potassium bichromate sulfuric acid solution to carry out surface oxidation treatment, takes out behind the immersion 20h and fully takes out residual potassium bichromate sulfuric acid solution with washed with de-ionized water.Concentrated stream road net after cleaning dries.
Embodiment 5
The concentrated sulfuric acid solution of preparation 200L 6mol/L is that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid, behind the dissolve complete solution is warming up to 60 ℃.Get and be of a size of 30000mm * 1067mm, thickness is that the polymethyl methacrylate material concentrated stream road net of 40mil places 60 ℃ potassium bichromate sulfuric acid solution to carry out surface oxidation treatment, takes out behind the immersion 15h and fully takes out residual potassium bichromate sulfuric acid solution with washed with de-ionized water.Concentrated stream road net after cleaning dries.
Embodiment 6
The concentrated sulfuric acid solution of preparation 200L 6mol/L is that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid, behind the dissolve complete solution is warming up to 80 ℃.Get and be of a size of 30000mm * 1067mm, thickness is that the polyurethane material concentrated stream road net of 1mil places 80 ℃ potassium bichromate sulfuric acid solution to carry out surface oxidation treatment, takes out behind the immersion 0.5h and fully takes out residual potassium bichromate sulfuric acid solution with washed with de-ionized water.Concentrated stream road net after cleaning dries.
Respectively with embodiment 1 and the concentrated stream road net of 2 described methods processing and the membrane module of untreated concentrated stream road net volume LP-4040 processed, each 2,4 altogether, be numbered modification concentrated stream road net 1, modification concentrated stream road net 2, common concentrated stream road net 1, common concentrated stream road net 2.Membrane module is put into monitor station, under standard conditions, move half an hour (225psi, 4000ppm NaCl, the rate of recovery 10%) and detect their flux and salt rejection rate.Preparation milk protein contaminated liquid, the water inlet take contaminated liquid as membrane component moves under standard conditions, and membrane module is polluted; After membrane module was contaminated, the aqueous slkali with 0.1% cleaned membrane module, tested their performance variation situation.Again dispose the milk protein contaminated liquid, the water inlet take contaminated liquid as membrane component moves under standard conditions, and membrane module is polluted; After membrane module was contaminated, the aqueous slkali with 0.1% cleaned membrane module, tested their performance variation situation.Each membrane module is in the process through twice pollution and alkali cleaning, and the concentrated stream road net desalination rate of change that test obtains sees Table 1, and concentrated stream road nethike embrane variations of flux rate sees Table 2.
Table 1 concentrated stream road net desalination rate of change
Table 2 concentrated stream road nethike embrane variations of flux rate
Table 1 is the desalination rate of change of 4 tested concentrated stream road nets, respective figure 1,2,3,4, and table 2 is the membrane flux rate of change of 4 tested concentrated stream road nets, respective figure 5,6,7,8.Fig. 1 is for adopting the membrane module desalination rate of change figure after embodiment 1 processes concentrated stream road net; Fig. 2 is for adopting the membrane module desalination rate of change figure after embodiment 2 processes concentrated stream road net; Fig. 3 is that concentrated stream road net is without the membrane module desalination rate of change figure of any processing; Fig. 4 is that concentrated stream road net is without the membrane module desalination rate of change figure of any processing; Fig. 5 is for adopting the membrane module membrane flux rate of change figure after embodiment 1 processes concentrated stream road net; Fig. 6 is for adopting the membrane module membrane flux rate of change figure after embodiment 2 processes concentrated stream road net; Fig. 7 is that concentrated stream road net is without the membrane module membrane flux rate of change figure of any processing; Fig. 8 is that concentrated stream road net is without the membrane module membrane flux rate of change figure of any processing.In the accompanying drawings: A is the desalination rate of change behind the pollution 2h, and B is the desalination rate of change behind the alkali cleaning 1h; C is the desalination rate of change behind the Re-pollution 2h; D is again the desalination rate of change behind the alkali cleaning 1h; E is the membrane flux rate of change behind the pollution 2h, and F is the membrane flux rate of change behind the alkali cleaning 1h; G is the membrane flux rate of change behind the Re-pollution 2h; H is again the membrane flux rate of change behind the alkali cleaning 1h.
By table 1, table 2 as can be known, the amplitude of variation of the membrane component modification concentrated stream road net 1 that rolls behind the employing embodiment of the invention method processing concentrated stream road net, the desalination rate of change of modification concentrated stream road net 2 is significantly less than common concentrated stream road net 1, common concentrated stream road net 2 without any processing; On the membrane flux, the difference of 4 tested concentrated stream road nets is then not obvious, illustrates that the membrane flux of whether processing membrane component through the inventive method does not then have much impacts.Generally speaking, the present invention can improve the salt rejection rate of membrane component and the stability of membrane flux, improves the resistant to pollution performance of reverse-osmosis membrane element.
Claims (4)
1. a method that improves the reverse-osmosis membrane element antifouling property is characterized in that utilizing the oxidation means that the concentrated stream road net of reverse-osmosis membrane element is processed, and strengthens concentrated stream road net hydrophily and reduces it to the adsorption capacity of pollutant.
2. a kind of method that improves the reverse-osmosis membrane element antifouling property according to claim 1 is characterized in that: mainly may further comprise the steps:
(1) preparation of Treatment Solution: the concentrated sulfuric acid solution of preparation 0.5～8mol/L;
(2) mass ratio by potassium bichromate and sulfuric acid is that 1:30 adds potassium bichromate;
(3) temperature of keeping treatment fluid is put into treatment fluid with concentrated stream road net and is soaked 0.5～24h at 40～90 ℃;
(4) take out concentrated stream road net water and rinse well, then concentrated stream road net thickness is dried or air-dry with hot blast.
3. a kind of method that improves the reverse-osmosis membrane element antifouling property according to claim 1 is characterized in that: the concentrated stream road net thickness 1～100mil in the described step (3).
4. a kind of method that improves the reverse-osmosis membrane element contamination resistance according to claim 1 is characterized in that: the concentrated stream road net in the described step (3) is by any or several composition the in polyethylene, polypropylene, polyacrylamide, polymethyl methacrylate, nylon and the polyurethane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365253A (en) * | 2016-08-31 | 2017-02-01 | 天津碧水源膜材料有限公司 | Method for preparing anti-pollution concentrated water runner net, application thereof and reverse osmosis device |
| CN115463549A (en) * | 2022-08-25 | 2022-12-13 | 万华化学集团股份有限公司 | Preparation method and application of membrane element water inlet runner net resistant to biological pollution |
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| CN1163793A (en) * | 1996-01-24 | 1997-11-05 | 日东电工株式会社 | High-permeability composite reverse osmosis membrane and reverse osmosis membrane assembly using same |
| CN1843590A (en) * | 2006-03-09 | 2006-10-11 | 佳尼特(上海)纯水设备有限公司 | Method for manufacturing high-flux reverse osmosis membrane element |
| JP2008029963A (en) * | 2006-07-28 | 2008-02-14 | Nitto Denko Corp | Water treatment method and apparatus |
| CN102320681A (en) * | 2011-06-22 | 2012-01-18 | 贵阳时代沃顿科技有限公司 | Antibacterial concentrated water isolating net and manufacture method thereof |
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2012
- 2012-12-04 CN CN201210514020.1A patent/CN102941019B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163793A (en) * | 1996-01-24 | 1997-11-05 | 日东电工株式会社 | High-permeability composite reverse osmosis membrane and reverse osmosis membrane assembly using same |
| CN1843590A (en) * | 2006-03-09 | 2006-10-11 | 佳尼特(上海)纯水设备有限公司 | Method for manufacturing high-flux reverse osmosis membrane element |
| JP2008029963A (en) * | 2006-07-28 | 2008-02-14 | Nitto Denko Corp | Water treatment method and apparatus |
| CN102320681A (en) * | 2011-06-22 | 2012-01-18 | 贵阳时代沃顿科技有限公司 | Antibacterial concentrated water isolating net and manufacture method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365253A (en) * | 2016-08-31 | 2017-02-01 | 天津碧水源膜材料有限公司 | Method for preparing anti-pollution concentrated water runner net, application thereof and reverse osmosis device |
| CN115463549A (en) * | 2022-08-25 | 2022-12-13 | 万华化学集团股份有限公司 | Preparation method and application of membrane element water inlet runner net resistant to biological pollution |
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Inventor after: Liang Songmiao Inventor after: Wu Zongce Inventor after: Jin Yan Inventor after: Tao Jian Inventor after: Xu Guoyang Inventor after: Cai Zhiqi Inventor before: Liang Songmiao Inventor before: Wu Zongce Inventor before: Jin Yan Inventor before: Tao Jian Inventor before: Xu Guoyang Inventor before: Cai Zhiqi |
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Address after: 550000 1518 Li Yang Avenue, Guiyang national hi tech Industrial Development Zone, Guiyang, Guizhou Patentee after: Time Walton Technology Co., Ltd. Address before: 550023 206, two / F, office building, South Guizhou science and Technology Industrial Park, Guiyang hi tech Zone. Patentee before: Vontron Technology Co., Ltd. |
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Effective date of registration: 20211203 Address after: 550008 No. 1518, Liyang Avenue, Guiyang National High tech Industrial Development Zone, Guiyang City, Guizhou Province Patentee after: Wharton Technology Co.,Ltd. Address before: 550000 1518 Li Yang Avenue, Guiyang national hi tech Industrial Development Zone, Guiyang, Guizhou Patentee before: VONTRON MEMBRANE TECHNOLOGY Co.,Ltd. |