CN102941019B - 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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- CN102941019B CN102941019B CN201210514020.1A CN201210514020A CN102941019B CN 102941019 B CN102941019 B CN 102941019B CN 201210514020 A CN201210514020 A CN 201210514020A CN 102941019 B CN102941019 B CN 102941019B
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- stream road
- 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 45
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 24
- 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 5
- 230000008569 process Effects 0.000 claims description 26
- 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
- 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
- 230000003647 oxidation Effects 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
- 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 39
- 238000010612 desalination reaction Methods 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 16
- 239000003513 alkali Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000010301 surface-oxidation reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011109 contamination Methods 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
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease 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
- 239000012466 permeate Substances 0.000 description 1
- 239000000047 product Substances 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
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- 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 improving reverse-osmosis membrane element antifouling property.
Background technology
In the use procedure of reverse osmosis membrane, due to the existence of the trapped substances such as Suspended Matter in Water, inorganic matter, organic matter, microorganism, while permeate is through film body, trapped substance must produce progressive pollution to film body.Excessive fouling membrane will make film properties decline, and even loses the due separation function of membranous system.Usually, the method preventing membrane component from polluting comprises: carry out pretreatment to former water, reduces suspension and content of organics in water; Regulate water inlet pH value, keep the stability of water, prevent from face forms dirt; Periodic cleaning is carried out to film; Stoppage in transit protection work is carried out time inactive; Regularly membrane component is changed.In addition, certain process can also be carried out to the concentrated stream road net in membrane component, to improve the resistant to pollution performance of membrane component, ensure that reverse osmosis membrane system can work continually and steadily.
Be separated, condensing protein or other large molecule solutes time, " gel layer " on film permeability rate impact very large.When flow velocity is certain and concentration polarization is not obvious, with the increase of pressure, near linear increases film permeability rate.After concentration polarization is worked, because pressure increases, permeability rate improves, and concentration polarization is thereupon serious, and permeability rate is improved and curved increase with pressure.After pressure is elevated to certain numerical value, concentration polarization make film surface solute concentration reach capacity concentration time, solute film surface separate out, formed " gel layer ".Now the permeability rate of " gel layer " resistance to film plays a decisive role, and permeability rate depends on pressure hardly.Therefore, to solute concentration one timing, should manage to avoid the formation of " gel layer ", to obtain 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 reverse osmosis membrane diaphragm rolls step by step, with the oxidant of different volumes concentration ratio, reverse osmosis membrane diaphragm is oxidized, makes reverse-osmosis membrane element compared with prior art have higher product discharge.The method carries out oxidation processes to the reverse osmosis membrane diaphragm in 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 improving reverse-osmosis membrane element antifouling property, solve the problem of membrane component antifouling property deficiency in prior art.
Technical scheme of the present invention is as described below.
Improving a method for reverse-osmosis membrane element antifouling property, is utilize the concentrated stream road net of oxidation means to reverse-osmosis membrane element to process, and strengthens concentrated stream road net hydrophily and reduces its adsorption capacity to pollutant.
The method of above-mentioned raising reverse-osmosis membrane element antifouling property, mainly comprises the following steps:
(1) preparation of Treatment Solution: the concentrated sulfuric acid solution of preparation 0.5 ~ 8mol/L;
(2) be that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid;
(3) maintain the temperature for the treatment of fluid at 40 ~ 90 DEG C, concentrated stream road net is put into treatment fluid and soak 0.5 ~ 24h;
(4) take out concentrated stream road net water to rinse well, then concentrated stream road net thickness to be dried or air-dry with hot blast.
Concentrated stream road net thickness 1 ~ 100mil in described step (3).
Concentrated stream road net in described step (3) is made up of any one or several in polyethylene, polypropylene, polyacrylamide, polymethyl methacrylate, nylon and polyurethane.
Beneficial effect of the present invention: carry out Strong oxdiative process to concentrated stream road net, effectively can improve the resistant to pollution performance of reverse-osmosis membrane element, improves the stability of salt rejection rate and membrane flux, is conducive to the life-span extending reverse osmosis membrane diaphragm.
Accompanying drawing explanation
Fig. 1 is the membrane module desalination rate of change figure after adopting embodiment 1 to process concentrated stream road net;
Fig. 2 is the membrane module desalination rate of change figure after adopting embodiment 2 to process concentrated stream road net;
Fig. 3 is the membrane module desalination rate of change figure of concentrated stream road net without any process;
Fig. 4 is the membrane module desalination rate of change figure of concentrated stream road net without any process;
Fig. 5 is the membrane module membrane flux rate of change figure after adopting embodiment 1 to process concentrated stream road net;
Fig. 6 is the membrane module membrane flux rate of change figure after adopting embodiment 2 to process concentrated stream road net;
Fig. 7 is the membrane module membrane flux rate of change figure of concentrated stream road net without any process;
Fig. 8 is the membrane module membrane flux rate of change figure of concentrated stream road net without any process;
In figure: A is the desalination rate of change after polluting 2h, and B is the desalination rate of change after alkali cleaning 1h; C is the desalination rate of change after again polluting 2h; D is again the desalination rate of change after alkali cleaning 1h; E is the membrane flux rate of change after polluting 2h, and F is the membrane flux rate of change after alkali cleaning 1h; G is the membrane flux rate of change after again polluting 2h; H is again the membrane flux rate of change after alkali cleaning 1h.
Detailed description of the invention
In order to deepen to understand the present invention, below in conjunction with embodiment, the present invention is described in further detail, and this embodiment only for explaining the present invention, does not form limiting the scope 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, dissolves solution warms to 70 DEG C completely.Get and be of a size of 30000mm × 1067mm, thickness is that the potassium bichromate sulfuric acid solution that the polypropylene material concentrated stream road net of 27mil is placed in 70 DEG C carries out surface oxidation treatment, and after soaking 2h, taking-up washed with de-ionized water fully takes out residual potassium bichromate sulfuric acid solution.Concentrated stream road net after cleaning adopts 60 DEG C of hot blasts air-dry.Concentrated stream road net after air-dry is rolled into the membrane module that specification is LP4040 together with counter-infiltration diaphragm and carries out follow-up performance and contamination resistance evaluation.
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, dissolves solution warms to 70 DEG C completely.Get and be of a size of 30000mm × 1067mm, thickness is that the potassium bichromate sulfuric acid solution that the polypropylene material concentrated stream road net of 27mil is placed in 70 DEG C carries out surface oxidation treatment, and after soaking 10h, taking-up washed with de-ionized water fully takes out residual potassium bichromate sulfuric acid solution.Concentrated stream road net after cleaning adopts 60 DEG C of hot blasts air-dry.Concentrated stream road net after air-dry is rolled into the membrane module that specification is LP4040 together with counter-infiltration diaphragm and carries out follow-up performance and contamination resistance evaluation.
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, dissolves solution warms to 90 DEG C completely.Get and be of a size of 30000mm × 1067mm, thickness is that the potassium bichromate sulfuric acid solution that the polyacrylamide material concentrated stream road net of 100mil is placed in 90 DEG C carries out surface oxidation treatment, and after soaking 24h, taking-up washed with de-ionized water fully takes out residual potassium bichromate sulfuric acid solution.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, dissolves solution warms to 50 DEG C completely.Get and be of a size of 30000mm × 1067mm, thickness is that the potassium bichromate sulfuric acid solution that the polyethylene material concentrated stream road net of 70mil is placed in 50 DEG C carries out surface oxidation treatment, and after soaking 20h, taking-up washed with de-ionized water fully takes out residual potassium bichromate sulfuric acid solution.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, dissolves solution warms to 60 DEG C completely.Get and be of a size of 30000mm × 1067mm, thickness is that the potassium bichromate sulfuric acid solution that the polymethyl methacrylate material concentrated stream road net of 40mil is placed in 60 DEG C carries out surface oxidation treatment, and after soaking 15h, taking-up washed with de-ionized water fully takes out residual potassium bichromate sulfuric acid solution.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, dissolves solution warms to 80 DEG C completely.Get and be of a size of 30000mm × 1067mm, thickness is that the potassium bichromate sulfuric acid solution that the polyurethane material concentrated stream road net of 1mil is placed in 80 DEG C carries out surface oxidation treatment, and after soaking 0.5h, taking-up washed with de-ionized water fully takes out residual potassium bichromate sulfuric acid solution.Concentrated stream road net after cleaning dries.
Respectively with the concentrated stream road net of method process and the membrane module of untreated concentrated stream road net volume LP-4040 described in embodiment 1 and 2, 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, runs flux and salt rejection rate that half an hour (225psi, 4000ppm NaCl, the rate of recovery 10%) detects them at the standard conditions.Preparation milk protein contaminated liquid, take contaminated liquid as the water inlet of membrane component, runs at the standard conditions, pollute membrane module; After membrane module is contaminated, with the aqueous slkali of 0.1%, membrane module is cleaned, test their performance change situation.Again configure milk protein contaminated liquid, take contaminated liquid as the water inlet of membrane component, run at the standard conditions, membrane module is polluted; After membrane module is contaminated, with the aqueous slkali of 0.1%, membrane module is cleaned, test their performance change 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 is in table 1, and concentrated stream road nethike embrane variations of flux rate is in 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 the membrane module desalination rate of change figure after adopting embodiment 1 to process concentrated stream road net; Fig. 2 is the membrane module desalination rate of change figure after adopting embodiment 2 to process concentrated stream road net; Fig. 3 is the membrane module desalination rate of change figure of concentrated stream road net without any process; Fig. 4 is the membrane module desalination rate of change figure of concentrated stream road net without any process; Fig. 5 is the membrane module membrane flux rate of change figure after adopting embodiment 1 to process concentrated stream road net; Fig. 6 is the membrane module membrane flux rate of change figure after adopting embodiment 2 to process concentrated stream road net; Fig. 7 is the membrane module membrane flux rate of change figure of concentrated stream road net without any process; Fig. 8 is the membrane module membrane flux rate of change figure of concentrated stream road net without any process.In the accompanying drawings: A is the desalination rate of change after polluting 2h, and B is the desalination rate of change after alkali cleaning 1h; C is the desalination rate of change after again polluting 2h; D is again the desalination rate of change after alkali cleaning 1h; E is the membrane flux rate of change after polluting 2h, and F is the membrane flux rate of change after alkali cleaning 1h; G is the membrane flux rate of change after again polluting 2h; H is again the membrane flux rate of change after alkali cleaning 1h.
From table 1, table 2, the amplitude of variation of the membrane component modification concentrated stream road net 1 rolled after adopting embodiment of the present invention method process concentrated stream road net, the desalination rate of change of modification concentrated stream road net 2, is significantly less than without the common concentrated stream road net 1 of any process, common concentrated stream road net 2; On membrane flux, the difference of 4 tested concentrated stream road nets is then not obvious, illustrates whether then do not have much impacts through the inventive method process to the membrane flux of membrane component.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 (3)
1. one kind is improved the method for reverse-osmosis membrane element antifouling property, it is characterized in that utilizing the concentrated stream road net of oxidation means to reverse-osmosis membrane element to process, strengthen concentrated stream road net hydrophily and reduce its adsorption capacity to pollutant, mainly comprising the following steps:
(1) preparation of Treatment Solution: the concentrated sulfuric acid solution of preparation 0.5 ~ 8mol/L;
(2) be that 1:30 adds potassium bichromate by the mass ratio of potassium bichromate and sulfuric acid;
(3) maintain the temperature for the treatment of fluid at 40 ~ 90 DEG C, concentrated stream road net is put into treatment fluid and soak 0.5 ~ 24h;
(4) take out concentrated stream road net water to rinse well, then concentrated stream road net thickness to be dried or air-dry with hot blast.
2. a kind of method improving reverse-osmosis membrane element antifouling property according to claim 1, is characterized in that: the concentrated stream road net thickness 1 ~ 100mil in described step (3).
3. a kind of method improving reverse-osmosis membrane element antifouling property according to claim 1, is characterized in that: the concentrated stream road net in described step (3) is made up of any one or several in polyethylene, polypropylene, polyacrylamide, polymethyl methacrylate, nylon and polyurethane.
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| CN201210514020.1A CN102941019B (en) | 2012-12-04 | 2012-12-04 | Method for improving anti-pollution performance of reverse osmosis membrane element |
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| 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 |
| CN115463549B (en) * | 2022-08-25 | 2024-06-25 | 万华化学集团股份有限公司 | Preparation method and application of membrane element water inlet runner network for resisting biological pollution |
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 |
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- 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 |
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