CN102753255A - Separation membrane modification method and separation membrane modification device - Google Patents
Separation membrane modification method and separation membrane modification device Download PDFInfo
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- CN102753255A CN102753255A CN2011800086149A CN201180008614A CN102753255A CN 102753255 A CN102753255 A CN 102753255A CN 2011800086149 A CN2011800086149 A CN 2011800086149A CN 201180008614 A CN201180008614 A CN 201180008614A CN 102753255 A CN102753255 A CN 102753255A
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- 239000012528 membrane Substances 0.000 title abstract description 122
- 238000000926 separation method Methods 0.000 title abstract description 23
- 230000004048 modification Effects 0.000 title description 26
- 238000012986 modification Methods 0.000 title description 26
- 238000002715 modification method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 73
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims description 182
- 238000009792 diffusion process Methods 0.000 claims description 182
- 239000007864 aqueous solution Substances 0.000 claims description 54
- 238000002407 reforming Methods 0.000 claims description 18
- 230000006866 deterioration Effects 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000012670 alkaline solution Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 176
- 238000001223 reverse osmosis Methods 0.000 description 82
- 239000013505 freshwater Substances 0.000 description 66
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 62
- 230000008595 infiltration Effects 0.000 description 34
- 238000001764 infiltration Methods 0.000 description 34
- 239000011780 sodium chloride Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000013535 sea water Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 230000004907 flux Effects 0.000 description 11
- 239000010865 sewage Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 238000001471 micro-filtration Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000012510 hollow fiber Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000021736 acetylation Effects 0.000 description 6
- 238000006640 acetylation reaction Methods 0.000 description 6
- 239000003651 drinking water Substances 0.000 description 6
- 235000020188 drinking water Nutrition 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000008400 supply water Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/162—Use of acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/164—Use of bases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0282—Dynamic pores-stimuli responsive membranes, e.g. thermoresponsive or pH-responsive
Abstract
Disclosed is a method for modifying a separation membrane comprising cellulose acetate so that the pores in the separation membrane are expanded within a short time and, at the same time, the deterioration of the separation membrane is suppressed. Specifically disclosed is a method for modifying a separation membrane comprising cellulose acetate, which is characterized by bringing the separation membrane into contact with an aqueous alkaline solution or an alcohol to expand the pores in the separation membrane.
Description
Technical field
The present invention relates to method of modifying and the reforming apparatus of diffusion barrier that a kind of micropore to diffusion barrier carries out the diffusion barrier of hole enlargement (diameter expansion).
Background technology
All the time; In the purified treatment of the desalination of seawater or waste water, used separate impurities films (for example reverse osmosis membrane (RO film), NF membrane (NF film), milipore filter (UF film), micro-filtration membrane (MF film) etc.) such as from former water (raw water), isolating ion, outstanding absurd creature matter.
But this diffusion barrier produces along with use, and impurity stops up, the cleaning of medicine etc. causes separation function, intensity to reduce, and therefore has necessary periodic replacement, produces the problem of a large amount of discarded objects.
From this viewpoint; The for example method of modifying of reverse osmosis membrane (for example patent documentation 1) has been proposed; Through on the supporting layer that forms by the filter membrane structure, forming the diffusion barrier that top layer with desalination function constitutes; Use oxidant (for example chlorine, hypochlorous acid, ozone, quaternary ammonium salt etc.) that this diffusion barrier is carried out oxidation processes, thereby remove the top layer of this diffusion barrier.
Remove the reverse osmosis membrane that the top layer obtains (RO film) through the method for modifying of this reverse osmosis membrane and for example be used as NF membrane (NF film), milipore filter (UF film), micro-filtration membrane (MF film) etc. and utilize again, thereby can realize reducing the discarded object amount.
Patent documentation 1: the spy of Japan opens the 2005-34723 communique
Summary of the invention
But; This diffusion barrier method of modifying is the method for modifying to polyamide system diffusion barrier; Inventor of the present invention is through to the diffusion barrier that formed by cellulose acetate this method on probation, find when it exists in micropore to the diffusion barrier that formed by cellulose acetate and carries out hole enlargement to grow the time, the problem of shortage practicality.In addition, this diffusion barrier method of modifying even can carry out hole enlargement to the micropore of this filter membrane, still exists and this micropore is carried out diffusion barrier after the hole enlargement because oxidation and deterioration causes this separations film strength reduction, the problem of lifetime.
In view of the above problems, a kind of can either be at short notice the micropore of the diffusion barrier that formed by cellulose acetate to be carried out method of modifying and the reforming apparatus of diffusion barrier of diffusion barrier that hole enlargement can reduce the deterioration of the diffusion barrier after this hole enlargement again be problem to provide in the present invention.
Diffusion barrier method of modifying of the present invention is characterised in that, contacts with alkaline aqueous solution through making the diffusion barrier that is formed by cellulose acetate, thereby the micropore of this diffusion barrier is carried out hole enlargement.
According to this diffusion barrier method of modifying, the ester bond of the acetyl group of cellulose acetate is by the alkaline aqueous solution hydrolysis, therefore can carry out hole enlargement to the micropore of the diffusion barrier that formed by cellulose acetate.And according to the method for modifying of such diffusion barrier, different with oxidation, hydrolysis damages diffusion barrier hardly, so diffusion barrier is difficult for deterioration.
In addition, diffusion barrier reforming apparatus of the present invention is characterised in that, is constituted as to contact with alkaline aqueous solution through the diffusion barrier that is formed by cellulose acetate and the micropore of this diffusion barrier is carried out hole enlargement.
In addition, the result of inventor's of the present invention research with keen determination finds that the micropore through the diffusion barrier that is formed by cellulose acetate is contacted with alcohol to this diffusion barrier carries out hole enlargement, thereby can carry out hole enlargement to this diffusion barrier at short notice.And find that the diffusion barrier deterioration that obtains through hole enlargement is few, and can carry out the film separation to processed water in high energy efficiency ground by the pore size comparison.And, so far accomplished the present invention.
Can think that in addition the mechanism of the micropore of this diffusion barrier being carried out hole enlargement through the diffusion barrier that formed by cellulose acetate contact with alcohol is considered to, owing to alcohol makes the cellulose acetate swelling, thereby micropore is by hole enlargement.
That is, diffusion barrier method of modifying of the present invention is characterised in that, contacts with alcohol through making the diffusion barrier that is formed by cellulose acetate, thereby the micropore of this diffusion barrier is carried out hole enlargement.
According to this diffusion barrier method of modifying, can be at short notice to forming by cellulose acetate and deterioration is few and can high energy efficiency ground processed water be carried out the diffusion barrier that diffusion barrier that film separates carries out hole enlargement by the pore size comparison.
In addition, diffusion barrier reforming apparatus of the present invention is characterised in that, is constituted as through the diffusion barrier that is formed by cellulose acetate to contact with alcohol and the micropore of this diffusion barrier is carried out hole enlargement.
As stated, according to the present invention, the deterioration of the diffusion barrier that can either suppress to be formed by cellulose acetate again can be at short notice carried out hole enlargement to the micropore of this diffusion barrier.
Description of drawings
Fig. 1 representes to possess the desalinization of using in the related diffusion barrier method of modifying of an embodiment to generate the schematic block diagram with the recycled water generating apparatus of reverse osmosis membrane (RO film) with the fresh water generating apparatus of reverse osmosis membrane (RO film) and the recycled water that possesses with the related diffusion barrier method of modifying preparation of an embodiment.
The specific embodiment
Followingly embodiment of the present invention is described with reference to accompanying drawing.
First embodiment
At first, the method for modifying of the diffusion barrier of first embodiment and the reforming apparatus of diffusion barrier are described.
The method of modifying of the diffusion barrier of first embodiment contacts with alkaline aqueous solution through making the diffusion barrier that is formed by cellulose acetate, thereby the micropore of this diffusion barrier is carried out hole enlargement.
In addition, in this specification, " modification of diffusion barrier " is meant the hole enlargement of the micropore of diffusion barrier.Thereby can confirm through the mode that makes diffusion barrier contact the NaCl salt rejection rate that has reduced diffusion barrier with alkaline aqueous solution through diffusion barrier is contacted come micropore to this diffusion barrier to carry out hole enlargement with alkaline aqueous solution.The NaCl salt rejection rate of diffusion barrier is NaCl solution (former water) is filtered and to obtain filter liquor with diffusion barrier, measures the NaCl concentration of former water and filter liquor, and brings these measured values into following formula and the value calculated.In addition, because NaCl concentration and the electrical conductivity relation of being in line also can replace measuring NaCl concentration with the mensuration electrical conductivity, and then calculate the NaCl salt rejection rate.
NaCl salt rejection rate (%)=(1-Cp/Cf) * 100
Cf: the NaCl concentration of former water, Cp: the NaCl concentration of filter liquor
Particularly, the diffusion barrier method of modifying of first embodiment is to causing desalinization that desalinization that separation function reduces with reverse osmosis membrane (RO film), perhaps used specified time limit (for example several years) to carry out hole enlargement with the micropore of reverse osmosis membrane (RO film) because of being used to utilize film to separate seawater is carried out fresh waterization to obtain fresh water such as drinking water.And; The diffusion barrier method of modifying of first embodiment carries out hole enlargement to this desalinization with the micropore of reverse osmosis membrane (RO film), and film separates and the recycled water that obtains recycled water generates with reverse osmosis membrane (RO film) thereby the sewage disposal water that obtains being used for obtaining utilizing active sludge treatment groove and equipment for separating liquid from solid that sewage is carried out purified treatment carries out.
In addition; Recycled water generates and compares with reverse osmosis membrane (RO film) with desalinization with reverse osmosis membrane (RO film); Do not require to obtain the high-purity infiltration water, but require to hang down the infiltration water that power obtains ormal weight, therefore; Generate with reverse osmosis membrane (RO film) as recycled water, using usually can enough film that filters with the lower power of reverse osmosis membrane (RO film) than desalinization.Therefore, desalinization being carried out reverse osmosis membrane (RO film) after the hole enlargement with the micropore of reverse osmosis membrane (RO film) can be applicable to as recycled water and generate with reverse osmosis membrane (RO film).
At this with reference to Fig. 1, to possessing above-mentioned desalinization with the fresh water generating apparatus of reverse osmosis membrane (RO film) and possess the recycled water generating apparatus that above-mentioned recycled water generates with reverse osmosis membrane (RO film) and describe.
As shown in Figure 1, fresh water generating apparatus 1 possesses: the fresh water generation, has milipore filter (UF film) or micro-filtration membrane (MF film), and seawater A is carried out filtration treatment and obtains infiltration water and condensed water B with film unit 11 with turbidity removal; Fresh water generates with a RO film unit 12, has reverse osmosis membrane (RO film), and carries out filtration treatment and obtain infiltration water and condensed water B with the infiltration water of turbidity removal after with film unit 11 seeing through this fresh water generation; And fresh water generates with the 2nd RO film unit 13, has reverse osmosis membrane (RO film), and carries out filtration treatment and obtain infiltration water and condensed water B with the infiltration water behind the RO film unit 12 seeing through this fresh water generation.
In addition; Above-mentioned fresh water generating apparatus 1 is constituted as: seawater A is generated with turbidity removal to fresh water shift with film unit 11; To generate to generate with a RO film unit 12 to fresh water through fresh water and shift with the infiltration water of turbidity removal after with film unit 11, will see through the fresh water generation with the infiltration water behind the RO film unit 12 to the fresh water generation with 13 transfers of the 2nd RO film unit.In addition, above-mentioned fresh water generating apparatus 1 is constituted as: will generate the condensed water B that each film unit of usefulness generates by fresh water and transfer to condensed water accumulator tank (not shown).And above-mentioned fresh water generating apparatus 1 is constituted as: will generate through above-mentioned fresh water and reclaim as fresh water C with the infiltration water behind the 2nd RO film unit 13.
Above-mentioned seawater A is the water of saliferous, is that for example salinity is the water of 1.0 ~ 8.0 quality %, more specifically, is that salinity is the water of 2.5 ~ 6.0 quality %.
In this specification, seawater A is not limited in and is present in marine water, so long as salinity surpasses the water of 1.0 quality %, comprises that also lake water (sabkha, brackish-water lake), bog water, Chi Shui etc. are present in the water on land.
As shown in Figure 1, recycled water generating apparatus 2 possesses: the recycled water generation, has milipore filter (UF film) or micro-filtration membrane (MF film), and above-mentioned sewage disposal water D is carried out filtration treatment, and obtain infiltration water and condensed water E with film unit 21 with turbidity removal; And recycled water generates with RO film unit 22, has reverse osmosis membrane (RO film), and carries out filtration treatment to seeing through above-mentioned recycled water generation with the infiltration water of turbidity removal after with film unit 21, and obtains infiltration water and condensed water E.
In addition, above-mentioned recycled water generating apparatus 2 is constituted as: above-mentioned sewage disposal water D is generated with turbidity removal to recycled water shift with film unit 21, will see through recycled water and generate with the infiltration water of turbidity removal after with film unit 21 to the recycled water generation with 22 transfers of RO film unit.In addition, above-mentioned recycled water generating apparatus 2 is constituted as: will generate the condensed water E that each film unit of usefulness generates by recycled water and shift to condensed water accumulator tank (not shown).And above-mentioned recycled water generating apparatus 2 is constituted as: will generate through above-mentioned recycled water and reclaim as recycled water F with the infiltration water behind the RO film unit 22.
In the method for modifying of the diffusion barrier of first embodiment; Make because of being used to utilize film to separate seawater A is carried out fresh waterization to contact with alkaline aqueous solution, thereby the micropore of this reverse osmosis membrane (RO film) is carried out hole enlargement with the reverse osmosis membrane (RO film) that the fresh water that obtains fresh water C such as drinking water and cause separation function to reduce generates with a RO film unit 12.And the method for modifying of the diffusion barrier of first embodiment carries out hole enlargement through the micropore to this reverse osmosis membrane (RO film), generates the reverse osmosis membrane (RO film) with RO film unit 22 thereby obtain recycled water.
The reverse osmosis membrane that above-mentioned fresh water generates with a RO film unit 12 is formed by cellulose acetate.In above-mentioned cellulose acetate, the quantity of the acetyl group that contains in the glucose unit is not special to be limited, but for example illustration 1 ~ 3, degree of acetylation is preferably 50 ~ 70%, more preferably about 61%.
At this, degree of acetylation is meant the combination acetic acid amount of per unit weight cellulose acetate, the value of trying to achieve according to the measurement and the calculating of degree of acetylation among the ASTM:D-817-91 (test methods of cellulose acetate etc.).
In addition, to generate the reverse osmosis membrane (RO film) with a RO film unit 12 be the film that for example forms the thread type that is called as hollow fiber membrane of the hollow of the tens of μ m of diameter ~ number mm for above-mentioned fresh water.
The pH of above-mentioned alkaline aqueous solution is 10 ~ 13, is preferably 11 ~ 13, more preferably 12 ~ 13.
Can enumerate out for example sodium hydrate aqueous solution, calcium hydroxide aqueous solution, ammonia spirit etc. as above-mentioned alkaline aqueous solution.
The method of modifying of the diffusion barrier of first embodiment; Through making alkaline aqueous solution generate supply port inflow with the supply water of a RO film unit 12 from fresh water; And alkaline aqueous solution is contacted with separation membrane surface, thereby the fresh water generation is carried out hole enlargement with the micropore of the reverse osmosis membrane (RO film) of a RO film unit 12 with the non-mode that sees through.In addition, alkaline aqueous solution generates with the supply of a RO film unit 12 to fresh water and also can carry out with the condensed water outlet of a RO film unit from the fresh water generation.
Method of modifying for the diffusion barrier of first embodiment; Using pH is 11 ~ 13 alkaline aqueous solution; And come the pore of fresh water generation with the reverse osmosis membrane (RO film) of a RO film unit 12 carried out in the mode of hole enlargement through above-mentioned contact; Be preferably 20 ~ 100 hours with the time of contact of alkaline aqueous solution, more preferably 20 ~ 50 hours.
The method of modifying of the diffusion barrier of first embodiment is like above-mentioned formation, and the reforming apparatus of the diffusion barrier of first embodiment is constituted as through the diffusion barrier that is formed by cellulose acetate is contacted with alkaline aqueous solution, thereby the micropore of this diffusion barrier is carried out hole enlargement.
In addition, though the reforming apparatus of the method for modifying of the diffusion barrier of first embodiment and diffusion barrier has said structure, the method for modifying of diffusion barrier of the present invention and the reforming apparatus of diffusion barrier are not limited to said structure, can suitably carry out design alteration.
For example, the method for modifying of the diffusion barrier of first embodiment is that the micropore to reverse osmosis membrane (RO film) carries out hole enlargement, also can carry out hole enlargement to the micropore of milipore filter (UF film), micro-filtration membrane diffusion barriers such as (MF films).In addition, reverse osmosis membrane comprises NF membrane (NF film).
In addition; Though in the method for modifying of the diffusion barrier of first embodiment; Micropore to the film of the type that is called as hollow fiber membrane carries out hole enlargement; But in the method for modifying of diffusion barrier of the present invention, also can carry out hole enlargement to having film or the micropore that is called as known diffusion barrier such as rolled film that is wound in envelope shape that web-like uses with the state that backing materials such as net are arranged in set inside when using of slightly counting the type that is called as tubular film of the rugosity about cm than above-mentioned hollow fiber membrane diameter.
And; Though in the diffusion barrier method of modifying of first embodiment; Making because of being used to utilize film to separate seawater A is carried out fresh waterization causes diffusion barrier that separation function reduces (particularly to obtain fresh water C such as drinking water; Fresh water generates the reverse osmosis membrane (RO film) with a RO film unit 12) micropore carry out hole enlargement, but the method for modifying of diffusion barrier of the present invention also can be to the diffusion barrier that causes the separation function reduction because of the various uses such as purified treatment that are used for waste water, used the micropore of the diffusion barrier of specified time limit (for example several years) to carry out hole enlargement.
In addition; Though in the method for modifying of the diffusion barrier of first embodiment; Prepare through above-mentioned hole enlargement and to be used for that above-mentioned sewage disposal water D is carried out film and to separate with the recycled water that obtains recycled water F and generate with reverse osmosis membrane (RO film) (the recycled water generation is with the reverse osmosis membrane (RO film) of RO film unit 22); But in the method for modifying of diffusion barrier of the present invention; So long as the diameter that can use micropore than micropore by the purposes of the big diffusion barrier of the diffusion barrier of the hole enlargement diameter of micropore (), can modification become to be used for the diffusion barrier of other purposes.In addition; In the method for modifying of diffusion barrier of the present invention; Be not limited to reverse osmosis membrane, so long as the diameter of micropore than micropore by the big diffusion barrier of the diffusion barrier of the hole enlargement diameter of micropore (), then also can modification become milipore filter (UF film), micro-filtration membrane diffusion barriers such as (MF films).In addition, reverse osmosis membrane (RO film) comprises NF membrane (NF film).
And the rate of change of the NaCl salt rejection rate of the method for modifying preferable separate film of the diffusion barrier of first embodiment is for greater than 0% and be below 70%, more preferably greater than 0% and be below 50%.
In addition, the rate of change of NaCl salt rejection rate is meant the value that is expressed from the next.In addition, also can replace NaCl with NaOH.
The rate of change of NaCl salt rejection rate (%)=[the NaCl salt rejection rate (%) of the diffusion barrier before (the NaCl salt rejection rate (%) of the diffusion barrier after NaCl salt rejection rate (the %)-hole enlargement of the diffusion barrier before the hole enlargement)/hole enlargement] * 100
Second embodiment
Then, the method for modifying of the diffusion barrier of second embodiment and the reforming apparatus of diffusion barrier are described.
Inventor of the present invention has carried out research with keen determination; The result finds; Carry out hole enlargement through the diffusion barrier that is formed by cellulose acetate is contacted with alkaline aqueous solution with the micropore to this diffusion barrier, thereby can not only suppress the deterioration of this diffusion barrier but also at short notice this diffusion barrier carried out hole enlargement.According to this method, the ester bond of the acetyl group of cellulose acetate is by the alkaline aqueous solution hydrolysis, therefore can carry out hole enlargement to the micropore of the diffusion barrier that formed by cellulose acetate.In addition, different with oxidation according to this method, owing to hydrolysis causes damage to diffusion barrier hardly, so diffusion barrier is difficult for deterioration.
Yet; For the diffusion barrier that is become the diameter of needs according to this method by hole enlargement; When during to this diffusion barrier force feed processed water, by the diffusion barrier after the hole enlargement relatively, not obtaining sufficiently high flux with the pressure of regulation; Therefore, must be in order to obtain required flux with high pressure more to diffusion barrier force feed processed water.That is,, exist to be difficult to high energy efficiency ground carries out the film separation to processed water problem for the diffusion barrier after this hole enlargement.
In view of the above problems, second embodiment with provide a kind of can be at short notice to forming by cellulose acetate and deterioration is few and can high energy efficiency ground processed water be carried out method of modifying and the reforming apparatus of diffusion barrier that diffusion barrier that film separates carries out the diffusion barrier of hole enlargement by the pore size comparison is problem.
The diffusion barrier method of modifying of second embodiment contacts with alcohol through making the diffusion barrier that is formed by cellulose acetate, thereby the micropore of this diffusion barrier is carried out hole enlargement.
In addition, in this manual, " modification of diffusion barrier " is meant the hole enlargement of the micropore of diffusion barrier.Thereby can confirm with the pure mode that contacts the NaCl salt rejection rate that has reduced diffusion barrier through making diffusion barrier through diffusion barrier and alcohol contacts come micropore to this diffusion barrier to carry out hole enlargement.The NaCl salt rejection rate of diffusion barrier is NaCl solution (former water) is filtered and to obtain filter liquor with diffusion barrier, measures the NaCl concentration of former water and filter liquor, and brings these measured values into following formula and the value calculated.In addition, because NaCl concentration and the electrical conductivity relation of being in line also can replace measuring NaCl concentration with the mensuration electrical conductivity, and then calculate the NaCl salt rejection rate.
NaCl salt rejection rate (%)=(1-Cp/Cf) * 100
Cf: the NaCl concentration of former water, Cp: the NaCl concentration of filter liquor
Particularly, the method for modifying of the diffusion barrier of second embodiment is to causing desalinization that desalinization that separation function reduces with reverse osmosis membrane (RO film), perhaps used specified time limit (for example several years) to carry out hole enlargement with the micropore of reverse osmosis membrane (RO film) because of being used to utilize film to separate seawater is carried out fresh waterization to obtain fresh water such as drinking water.And; The method of modifying of the diffusion barrier of second embodiment carries out hole enlargement to this desalinization with the micropore of reverse osmosis membrane (RO film), and film separates and the recycled water that obtains recycled water generates with reverse osmosis membrane (RO film) thereby the sewage disposal water that obtains being used for obtaining utilizing active sludge treatment groove and equipment for separating liquid from solid that sewage is carried out purified treatment carries out.
In addition; Recycled water generates and compares with reverse osmosis membrane (RO film) with desalinization with reverse osmosis membrane (RO film); Do not require to obtain the high-purity infiltration water, but require to hang down the infiltration water that power obtains ormal weight, therefore; Generate with reverse osmosis membrane (RO film) as recycled water, using usually can enough film that filters with the lower power of reverse osmosis membrane (RO film) than desalinization.Therefore, the reverse osmosis membrane (RO film) that desalinization has been carried out hole enlargement with the micropore of reverse osmosis membrane (RO film) can be applicable to as recycled water and generate with reverse osmosis membrane (RO film).
At this with reference to Fig. 1, to possessing above-mentioned desalinization with the fresh water generating apparatus of reverse osmosis membrane (RO film) and possess the recycled water generating apparatus that above-mentioned recycled water generates with reverse osmosis membrane (RO film) and describe.
As shown in Figure 1, fresh water generating apparatus 1 possesses: the fresh water generation, has milipore filter (UF film) or micro-filtration membrane (MF film), and seawater A is carried out filtration treatment and obtains infiltration water and condensed water B with film unit 11 with turbidity removal; Fresh water generates with a RO film unit 12, has reverse osmosis membrane (RO film), and carries out filtration treatment and obtain infiltration water and condensed water B with the infiltration water of turbidity removal after with film unit 11 seeing through this fresh water generation; And fresh water generates with the 2nd RO film unit 13, has reverse osmosis membrane (RO film), and carries out filtration treatment and obtain infiltration water and condensed water B with the infiltration water behind the RO film unit 12 seeing through this fresh water generation.
In addition; Above-mentioned fresh water generating apparatus 1 is constituted as: seawater A is generated with turbidity removal to fresh water shift with film unit 11; To generate to generate with a RO film unit 12 to fresh water through fresh water and shift with the infiltration water of turbidity removal after with film unit 11, will see through the fresh water generation with the infiltration water behind the RO film unit 12 to the fresh water generation with 13 transfers of the 2nd RO film unit.In addition, above-mentioned fresh water generating apparatus 1 is constituted as: will generate the condensed water B that each film unit of usefulness generates by fresh water and transfer to condensed water accumulator tank (not shown).And above-mentioned fresh water generating apparatus 1 is constituted as: will generate through above-mentioned fresh water and reclaim as fresh water C with the infiltration water behind the 2nd RO film unit 13.
Above-mentioned seawater A is the water of saliferous, is that for example salinity is the water of 1.0 ~ 8.0 quality %, more specifically, is that salinity is the water of 2.5 ~ 6.0 quality %.
In this specification, seawater A is not limited in and is present in marine water, so long as salinity surpasses the water of 1.0 quality %, comprises that also lake water (sabkha, brackish-water lake), bog water, Chi Shui etc. are present in the water on land.
As shown in Figure 1, recycled water generating apparatus 2 possesses: the recycled water generation, has milipore filter (UF film) or micro-filtration membrane (MF film), and above-mentioned sewage disposal water D is carried out filtration treatment, and obtain infiltration water and condensed water E with film unit 21 with turbidity removal; And recycled water generates with RO film unit 22, has reverse osmosis membrane (RO film), and carries out filtration treatment to seeing through above-mentioned recycled water generation with the infiltration water of turbidity removal after with film unit 21, and obtains infiltration water and condensed water E.
In addition, above-mentioned recycled water generating apparatus 2 is constituted as: above-mentioned sewage disposal water D is generated with turbidity removal to recycled water shift with film unit 21, will see through recycled water and generate with the infiltration water of turbidity removal after with film unit 21 to the recycled water generation with 22 transfers of RO film unit.In addition, above-mentioned recycled water generating apparatus 2 is constituted as: will generate the condensed water E that each film unit of usefulness generates by recycled water and shift to condensed water accumulator tank (not shown).And above-mentioned recycled water generating apparatus 2 is constituted as: will generate through above-mentioned recycled water and reclaim as recycled water F with the infiltration water behind the RO film unit 22.
In the method for modifying of the diffusion barrier of second embodiment; Make because of being used to utilize film to separate seawater A is carried out fresh waterization to contact with alcohol solution, thereby the micropore of this reverse osmosis membrane (RO film) is carried out hole enlargement with the reverse osmosis membrane (RO film) that the fresh water that obtains fresh water C such as drinking water and cause separation function to reduce generates with a RO film unit 12.And the method for modifying of the diffusion barrier of second embodiment carries out hole enlargement through the micropore to this reverse osmosis membrane (RO film), generates the reverse osmosis membrane (RO film) with RO film unit 22 thereby obtain recycled water.
The reverse osmosis membrane that above-mentioned fresh water generates with a RO film unit 12 is formed by cellulose acetate.In above-mentioned cellulose acetate, the quantity of the acetyl group that contains in the glucose unit is not special to be limited, but for example illustration 1 ~ 3, degree of acetylation is preferably 50 ~ 70%, more preferably about 61%.
At this, degree of acetylation is meant the combination acetic acid amount of per unit weight cellulose acetate, the value of trying to achieve according to the measurement and the calculating of degree of acetylation among the ASTM:D-817-91 (test methods of cellulose acetate etc.).
In addition, to generate the reverse osmosis membrane (RO film) with a RO film unit 12 be the film that for example forms the thread type that is called as hollow fiber membrane of the hollow of the tens of μ m of diameter ~ number mm for above-mentioned fresh water.
As above-mentioned alcohol, can enumerate out for example methyl alcohol, ethanol, propyl alcohol etc.
The diffusion barrier method of modifying of second embodiment; Through making alcohol generate supply port inflow with the supply water of a RO film unit 12 from fresh water; And alcohol is contacted with separation membrane surface, thereby the fresh water generation is carried out hole enlargement with the micropore of the reverse osmosis membrane (RO film) of a RO film unit 12 with the non-mode that sees through.In addition, alcohol solution generates with the supply of a RO film unit to fresh water and also can carry out with the condensed water outlet of a RO film unit from the fresh water generation.
The method of modifying of the diffusion barrier of second embodiment; Preferred 10 ~ 90 volume % that use; Be more preferably the alcohol solution of 40 ~ 60 volume %; And come the micropore that fresh water generates with the reverse osmosis membrane (RO film) of a RO membrane module 12 is carried out in the mode of hole enlargement through contact above-mentioned, be preferably set to 5 minutes with time of contact of alcohol solution ~ 100 hours, more preferably 10 minutes ~ 50 hours.
The method of modifying of the diffusion barrier of second embodiment is like above-mentioned formation, and the reforming apparatus of the diffusion barrier of second embodiment is constituted as through the diffusion barrier that is formed by cellulose acetate is contacted with alcohol, thereby the micropore of this diffusion barrier is carried out hole enlargement.
In addition, though the reforming apparatus of the method for modifying of the diffusion barrier of second embodiment and diffusion barrier has said structure, the method for modifying of diffusion barrier of the present invention and the reforming apparatus of diffusion barrier are not limited to said structure, can suitably carry out design alteration.
For example, the method for modifying of the diffusion barrier of second embodiment is that the micropore to reverse osmosis membrane (RO film) carries out hole enlargement, also can carry out hole enlargement to the micropore of milipore filter (UF film), micro-filtration membrane diffusion barriers such as (MF films).In addition, reverse osmosis membrane comprises NF membrane (NF film).
In addition; Though in the method for modifying of the diffusion barrier of second embodiment; Micropore to the film of the type that is called as hollow fiber membrane carries out hole enlargement; But in the method for modifying of diffusion barrier of the present invention, also can carry out hole enlargement to having film or the micropore that is called as known diffusion barrier such as rolled film that is wound in envelope shape that web-like uses with the state that backing materials such as net are arranged in set inside when using of slightly counting the type that is called as tubular film of the rugosity about cm than above-mentioned hollow fiber membrane diameter.
And; Though in the diffusion barrier method of modifying of second embodiment; Making because of being used to utilize film to separate seawater A is carried out fresh waterization causes diffusion barrier that separation function reduces (particularly to obtain fresh water C such as drinking water; Fresh water generates the reverse osmosis membrane (RO film) with a RO film unit 12) micropore carry out hole enlargement, but the method for modifying of diffusion barrier of the present invention also can be to the diffusion barrier that causes the separation function reduction because of the various uses such as purified treatment that are used for waste water, used the micropore of the diffusion barrier of specified time limit (for example several years) to carry out hole enlargement.
In addition; Though in the method for modifying of the diffusion barrier of second embodiment; Prepare through above-mentioned hole enlargement and to be used for that above-mentioned sewage disposal water D is carried out film and to separate with the recycled water that obtains recycled water F and generate with reverse osmosis membrane (RO film) (the recycled water generation is with the reverse osmosis membrane (RO film) of RO film unit 22); But in the method for modifying of diffusion barrier of the present invention; So long as the diameter that can use micropore than micropore by the purposes of the big diffusion barrier of the diffusion barrier of the hole enlargement diameter of micropore (), can modification become to be used for the diffusion barrier of other purposes.In addition; In the method for modifying of diffusion barrier of the present invention; Be not limited to reverse osmosis membrane, so long as the diameter of micropore than micropore by the big diffusion barrier of the diffusion barrier of the hole enlargement diameter of micropore (), then also can modification become milipore filter (UF film), micro-filtration membrane diffusion barriers such as (MF films).In addition, reverse osmosis membrane (RO film) comprises NF membrane (NF film).
And the rate of change of the NaCl salt rejection rate of the method for modifying preferable separate film of the diffusion barrier of second embodiment is for greater than 0% and be below 90%, more preferably greater than 0% and be below 80%.
In addition, the rate of change of NaCl salt rejection rate is meant the value that is expressed from the next.
The rate of change of NaCl salt rejection rate (%)=[the NaCl salt rejection rate (%) of the diffusion barrier before (the NaCl salt rejection rate (%) of the diffusion barrier after NaCl salt rejection rate (the %)-hole enlargement of the diffusion barrier before the hole enlargement)/hole enlargement] * 100
Embodiment
Then, enumerating 1 to 3 couple of the present invention of test further specifies.
(test 1: alkaline aqueous solution and acidic aqueous solution, high-temperature water and contain the comparison of aqueous oxidizing agent solution)
(routine 1-1: alkaline aqueous solution)
Will be from having RO film unit (Japan's textile company system of the reverse osmosis membrane (RO film) that forms by cellulose acetate; Trade name: the hollow-fibre membrane that ホ ロ セ ッ プ (HB10255FI)) cuts out impregnated in (sodium hydrate aqueous solution of PH13) in the alkaline aqueous solution, makes its contact time of contact according to table 1.In addition, be meant the meaning that reverse osmosis membrane (RO film) do not contact with alkaline aqueous solution (also be same case 0 hour time of contact in the example 3) 0 hour time of contact in the following table.
Then; Each is applied the pressure shown in the table 1 (intermembranous pressure reduction) by time of contact of table 1 with reverse osmosis membrane (RO film) after alkaline aqueous solution contacts; The flow of condensed water is that the mode of 1L/min is supplied with pure water from the supply port of the supply water of RO film unit filters with distributary, and the amount of measuring infiltration water reaches the time (time of penetration) till the 25mL.The result is shown in table 1.
[table 1]
※ represented more than 60 minutes.
(routine 1-2: acidic aqueous solution)
Except use acidic aqueous solution (5 quality % aqueous sulfuric acid) replace alkaline aqueous solution and time of contact as shown in table 2; With the method identical acidic aqueous solution is contacted with reverse osmosis membrane (RO film), then measure the time of penetration of pure water with the method identical with routine 1-1 with routine 1-1.The result is shown in table 2.
[table 2]
(routine 1-3: high-temperature water)
Except using running water to replace alkaline aqueous solution; And the running water (high-temperature water) this running water being kept make under 90 ℃ the state diffusion barrier with 90 ℃ contacts; And time of contact as shown in table 3 beyond; With the method identical high-temperature water is contacted with reverse osmosis membrane (RO film), then measure the time of penetration of pure water with the method identical with routine 1-1 with routine 1-1.The result is shown in table 3.
[table 3]
(routine 1-4: contain aqueous oxidizing agent solution)
Except containing aqueous oxidizing agent solution (the hypochlorous aqueous solution of 200ppm), use replaces alkaline aqueous solution; And time of contact as shown in table 4 beyond; Make with the method identical to contain aqueous oxidizing agent solution and contact, then measure the time of penetration of pure water with the method identical with routine 1-1 with reverse osmosis membrane (RO film) with routine 1-1.The result is shown in table 4.
[table 4]
Like table 1 to shown in 4; Be illustrated in when using alkaline aqueous solution; Compare with the situation of using high-temperature water, acidic aqueous solution, contain aqueous oxidizing agent solution, can shorten the time of penetration of the diffusion barrier that forms by cellulose acetate, promptly can carry out hole enlargement the micropore of diffusion barrier.
In addition, when using alkaline aqueous solution, think 3 hours and still enlarging the aperture afterwards, but think that the intensity of material reduces, owing to pressure is difficult to keep the macaroni yarn shape, runner stops up.
(test 2: the comparison of alkaline aqueous solution and alcohol solution)
(routine 2-1: alkaline aqueous solution, time of contact: 48h)
Use 180 from RO film unit with the reverse osmosis membrane (RO film) that forms by Triafol T (Japan's textile company system, trade name: the hollow fiber membrane that ホ ロ セ ッ プ (HB10255FI)) cuts out is prepared into small-sized RO membrane module.Alkaline aqueous solution (pH:12.7, the NaOH aqueous solution of electrical conductivity: 5mS/cm) is flowed into from the supply port of the supply water of small-sized RO membrane module, make alkaline aqueous solution contact 48 hours with reverse osmosis membrane (RO film) with the non-mode that sees through.
Then; Reverse osmosis membrane after the modification (RO film) is applied the operating pressure (intermembranous pressure reduction) of table 5; The flow of condensed water is that the mode of 1L/min is supplied with pure water from the supply port of the supply water of RO membrane module filters with distributary, measures amount (the pure water Flux: pure water flux) of the infiltration water of gained in 10 minutes.
In addition; To before the modification and the reverse osmosis membrane (RO film) after the modification apply the operating pressure (intermembranous pressure reduction) of table 5; The flow of condensed water is that the mode of 1L/min is supplied with the NaCl aqueous solution (NaCl concentration: 6 quality %), measure the amount (NaCl-Flux:NaCl flux) of the infiltration water of gained in 10 minutes from the supply port of the supply water of RO film unit filters with distributary.In addition, also measured as the electrical conductivity (NaCl electrical conductivity) of the NaCl aqueous solution of supplying with water and the electrical conductivity of infiltration water.
In addition, likewise identical with reverse osmosis membrane (RO film) after the modification, the reverse osmosis membrane before the modification (RO film) is also carried out identical measurement.
This test is carried out 3 times repeatedly.The result is shown in table 5.In addition, pure water flux (Flux) increment rate is represented the ratio of pure water flux of pure water flux and the reverse osmosis membrane (RO film) before the modification of the reverse osmosis membrane (RO film) after the modification.Also identical in other tables.
[table 5]
(routine 2-2: alcohol solution, time of contact: 20min)
Except use alcohol solution (50 volume % ethanol water) replaces alkaline aqueous solution, and change into time of contact beyond the 20min, make an experiment with the method identical with routine 2-1.The result is shown in table 6.
[table 6]
(routine 2-3: alcohol solution, time of contact: 24h)
Except changing into time of contact the 24h, make an experiment with the method identical with routine 2-2.The result is shown in table 7.
[table 7]
As shown in table 5, through using alkaline aqueous solution to carry out modification 48 hour time of contact, 1.3 times of pure water flux increment rate average out to, the rate of change average out to 37.1% of NaCl salt rejection rate.On the other hand, through using the alcohol solution contact to carry out modification, 1.9 times of pure water flux increment rate average out to, the rate of change average out to 29.9% of NaCl salt rejection rate in 24 hours.Show thus, used the modification of alcohol solution to compare, relatively can carry out the film separation to processed water in high energy efficiency ground by size with the modification of having used alkaline aqueous solution.
Also show, used the modification of alcohol solution the same, can shorten the time of penetration of the diffusion barrier that forms by cellulose acetate, promptly can carry out hole enlargement the micropore of diffusion barrier with the modification of having used alkaline aqueous solution.
And, identical for the modification of having used alcohol solution with the modification of having used alkaline aqueous solution, all do not observe the deterioration of the diffusion barrier that forms by cellulose acetate.
(test 3)
Except use the NaOH aqueous solution (pH:12.7, electrical conductivity: 5mS/cm) replace the NaCl aqueous solution, and modification time as shown in table 8 beyond, to modification, carry out and test the identical test of in 2 the NaCl aqueous solution being carried out of test based on alkaline aqueous solution.
This test is carried out 3 times repeatedly.The result is shown in table 8.
[table 8]
As shown in table 8 showing, the long more modification progress of modification time degree is big more.
Symbol description
1: fresh water generating apparatus, 2: the recycled water generating apparatus
11: fresh water generates with turbidity removal with film unit, 12: fresh water generates with a RO film unit
13: fresh water generates with the 2nd RO film unit, 21: recycled water generates and uses film unit with turbidity removal
22: recycled water generates with RO film unit, A: seawater
B: condensed water, C: fresh water, D: sewage disposal water
E: condensed water, F: recycled water
Claims (4)
1. the method for modifying of a diffusion barrier is characterized in that,
Through the diffusion barrier that is formed by cellulose acetate is contacted with alkaline aqueous solution, thereby the micropore of this diffusion barrier is carried out hole enlargement.
2. the reforming apparatus of a diffusion barrier is characterized in that,
Said reforming apparatus is constituted as and contacts with alkaline aqueous solution through the diffusion barrier that is formed by cellulose acetate and the micropore of this diffusion barrier is carried out hole enlargement.
3. the method for modifying of a diffusion barrier is characterized in that,
Through the diffusion barrier that formed by cellulose acetate is contacted with alcohol, thereby the micropore of this diffusion barrier is carried out hole enlargement.
4. the reforming apparatus of a diffusion barrier is characterized in that,
Said reforming apparatus is constituted as through the diffusion barrier that formed by cellulose acetate and contacts with alcohol and the micropore of this diffusion barrier is carried out hole enlargement.
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| JP2010039877A JP5222869B2 (en) | 2010-02-25 | 2010-02-25 | Separation membrane reforming method and separation membrane reforming apparatus |
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| JP2010-098695 | 2010-04-22 | ||
| JP2010098695A JP5222886B2 (en) | 2010-04-22 | 2010-04-22 | Separation membrane reforming method and separation membrane reforming apparatus |
| PCT/JP2011/052312 WO2011105188A1 (en) | 2010-02-25 | 2011-02-04 | Separation membrane modification method and separation membrane modification device |
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| CN109200615A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of processing method preparing produced tail gas during hydrogen peroxide |
| CN109200772A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | The processing method of tail gas during butane cis-butenedioic anhydride |
| CN109985529A (en) * | 2018-11-29 | 2019-07-09 | 福建工程学院 | A kind of preparation method and application method of amphipathic water-oil separating filter membrane |
| CN112452161A (en) * | 2020-11-26 | 2021-03-09 | 四川大学 | Hydrophilic membrane and preparation method thereof |
| CN113461109A (en) * | 2021-08-02 | 2021-10-01 | 广东工业大学 | Multistage reverse osmosis process and system capable of regulating and controlling desalination rate |
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| CN107376666B (en) * | 2017-08-09 | 2019-08-02 | 中国农业大学 | A kind of modified cellulose acetate film and the preparation method and application thereof |
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| CN109200772A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | The processing method of tail gas during butane cis-butenedioic anhydride |
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| CN113461109A (en) * | 2021-08-02 | 2021-10-01 | 广东工业大学 | Multistage reverse osmosis process and system capable of regulating and controlling desalination rate |
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| WO2011105188A1 (en) | 2011-09-01 |
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