CN102753255B - 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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- CN102753255B CN102753255B CN201180008614.9A CN201180008614A CN102753255B CN 102753255 B CN102753255 B CN 102753255B CN 201180008614 A CN201180008614 A CN 201180008614A CN 102753255 B CN102753255 B CN 102753255B
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- seperation film
- seperation
- reverse osmosis
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- 238000000926 separation method Methods 0.000 title claims abstract description 41
- 239000012528 membrane Substances 0.000 title abstract description 128
- 230000004048 modification Effects 0.000 title description 15
- 238000012986 modification Methods 0.000 title description 15
- 238000002715 modification method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 72
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 193
- 239000013505 freshwater Substances 0.000 claims description 68
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 63
- 239000007864 aqueous solution Substances 0.000 claims description 53
- 230000008929 regeneration Effects 0.000 claims description 41
- 238000011069 regeneration method Methods 0.000 claims description 41
- 230000006866 deterioration Effects 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 238000001223 reverse osmosis Methods 0.000 description 82
- 230000008595 infiltration Effects 0.000 description 24
- 238000001764 infiltration Methods 0.000 description 24
- 239000011780 sodium chloride Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000013535 sea water Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000002407 reforming Methods 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- 238000001471 micro-filtration Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 239000012510 hollow fiber Substances 0.000 description 7
- 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
- 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
- 238000010612 desalination reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920006221 acetate fiber Polymers 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design 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
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000010865 sewage Substances 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-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
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 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
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 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
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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 a kind of micropore to seperation film carry out expanding（diameter expansion）The changing of seperation film
Property method and the reforming apparatus of seperation film.
Background technology
All the time, in the desalination of sea water or the purified treatment of waste water, employ from raw water（Raw water）In point
Separate out the seperation film of the impurity such as ion, suspended material（Such as reverse osmosis membrane（RO film）, NF membrane（NF film）, ultrafilter membrane（UF film）、
Micro-filtration membrane（MF film）Deng）.
But this seperation film produces impurity blocking, cleaning of medicine etc. and causes separation function, intensity fall with using
Low, therefore exist and must regularly replace, produce the problem of a large amount of garbages.
From this viewpoint it is proposed that the method for modifying of such as reverse osmosis membrane（Such as patent documentation 1）, by by
Filter the seperation film top layer with desalination function being formed on the supporting layer that film structure is formed and constituting, using oxidant（Example
As chlorine, hypochlorous acid, ozone, quaternary ammonium salt etc.）Oxidation processes are carried out to this seperation film, thus removing the top layer of this seperation film.
Reverse osmosis membrane obtained from top layer is eliminated by the method for modifying of this reverse osmosis membrane（RO film）By as example
NF membrane（NF film）, ultrafilter membrane（UF film）, micro-filtration membrane（MF film）Deng and recycle such that it is able to realize reduce garbage amount.
Patent documentation 1：Japanese Laid-Open 2005-34723 publication
Content of the invention
But, this seperation film method of modifying is the method for modifying for polyamide seperation film, the present inventor
By trying to the seperation film being formed by cellulose acetate in this way, to find that it exists to dividing of being formed by cellulose acetate
From the micropore of film carry out expanding when wanted time length, lack practicality problem.In addition, this seperation film method of modifying, even if
The micropore of this filter membrane can be carried out expanding, however it remains this micropore is carried out expanding after seperation film bad due to oxidation
Change, lead to the intensity decreases of this seperation film, the problem of lifetime.
In view of the above problems, the present invention with provide a kind of can either be at short notice to the separation being formed by cellulose acetate
The micropore of film carry out expanding and can reduce this expanding after the method for modifying of the seperation film of the deterioration of seperation film and seperation film
Reforming apparatus be problem.
The seperation film method of modifying of the present invention is characterised by, by making the seperation film and the alkalescence that are formed by cellulose acetate
Aqueous solution contacts, thus carry out expanding to the micropore of this seperation film.
According to this seperation film method of modifying, the ester bond of the acetyl group of cellulose acetate is hydrolyzed by alkaline aqueous solution, therefore
The micropore of the seperation film being formed by cellulose acetate can be carried out expanding.And, according to the method for modifying of such seperation film,
Different from aoxidizing, hydrolysis hardly damages to seperation film, and therefore seperation film is not easily deteriorated.
In addition, the seperation film reforming apparatus of the present invention are characterised by, it is configured to by being formed by cellulose acetate
Seperation film is contacted with alkaline aqueous solution and the micropore of this seperation film is carried out expanding.
In addition, the present inventor research with keen determination is it was found that by making the separation being formed by cellulose acetate
Film is contacted with alcohol and carries out expanding such that it is able to carry out to this seperation film expanding at short notice to the micropore of this seperation film.And
And find, few by seperation film deterioration obtained from expanding, and by pore size compare can high energy efficiency to processed water
Carry out membrance separation.And, so far complete the present invention.
Can be additionally considered to, by making to be contacted and the micropore to this seperation film with alcohol by the seperation film that cellulose acetate is formed
Carrying out expanding mechanism is considered as, because alcohol makes cellulose acetate swelling, thus micropore is expanding.
That is, the seperation film method of modifying of the present invention is characterised by, by make the seperation film that formed by cellulose acetate with
Alcohol contacts, thus carry out expanding to the micropore of this seperation film.
According to this seperation film method of modifying, can be at short notice to being formed and deteriorated less and by hole by cellulose acetate
Footpath size compares and high energy efficiency processed water can be carried out with the seperation film of membrance separation carries out expanding seperation film.
In addition, the seperation film reforming apparatus of the present invention are characterised by, it is configured to by being formed by cellulose acetate
Seperation film is contacted with alcohol and the micropore of this seperation film is carried out expanding.
As described above, according to the present invention, can either suppress the deterioration of seperation film that formed by cellulose acetate again can be
In short time, the micropore of this seperation film is carried out expanding.
Brief description
Fig. 1 is to represent desalinization reverse osmosiss used in the seperation film method of modifying possessing involved by an embodiment
Film（RO film）Device for generating fresh water and possess with involved by an embodiment seperation film method of modifying preparation recycled water
Generation reverse osmosis membrane（RO film）Regeneration water generating device schematic block diagram.
Specific embodiment
Referring to the drawings embodiments of the present invention are illustrated.
First embodiment
First, the reforming apparatus of the method for modifying to the seperation film of first embodiment and seperation film illustrate.
The method of modifying of the seperation film of first embodiment, by making the seperation film and the alkaline water that are formed by cellulose acetate
Solution contacts, thus carry out expanding to the micropore of this seperation film.
In addition, in this specification, " modification of seperation film " refers to the expanding of the micropore of seperation film.By making seperation film and alkali
Property aqueous solution contact the micropore of this seperation film carried out expanding can by making seperation film contact with alkaline aqueous solution thus
The mode of NaCl salt rejection rate reducing seperation film is determining.The NaCl salt rejection rate of seperation film is to NaCl solution with seperation film
（Raw water）Filtered and obtained filter liquor, measure the NaCl concentration of raw water and filter liquor, and these measured values are brought into down
Formula and the value that calculates.The relation further, since NaCl concentration and electric conductivity are in line is it is also possible to be replaced with mensure electric conductivity measuring
NaCl concentration, and then calculate NaCl salt rejection rate.
NaCl salt rejection rate（%）=（1-Cp/Cf）×100
Cf：The NaCl concentration of raw water, Cp：The NaCl concentration of filter liquor
Specifically, the seperation film method of modifying of first embodiment is to because for carrying out fresh water using membrance separation to sea water
Change the desalinization reverse osmosis membrane causing separation function to reduce to obtain the fresh water such as drinking water（RO film）Or employ rule
Between periodically（The such as several years）Desalinization reverse osmosis membrane（RO film）Micropore carry out expanding.And, first embodiment
Seperation film method of modifying is to this desalinization reverse osmosis membrane（RO film）Micropore carry out expanding, thus obtain for using live
Property Treatment of Sludge groove and equipment for separating liquid from solid sewage is carried out recycled treated water obtained from purified treatment carry out membrance separation and
Regeneration water generating reverse osmosis membrane to recycled water（RO film）.
In addition, regeneration water generating reverse osmosis membrane（RO film）With desalinization reverse osmosis membrane（RO film）Compare, do not require
Obtain high-purity infiltration water, but require to obtain the infiltration water of ormal weight compared with low dynamics, accordingly, as regeneration water generating reverse osmosis
Permeable membrane（RO film）, being usually used can be with than desalinization reverse osmosis membrane（RO film）The film that more low dynamics are filtered.Therefore,
To desalinization reverse osmosis membrane（RO film）Micropore carry out expanding after reverse osmosis membrane（RO film）Can be suitable as regenerating
Water generating reverse osmosis membrane（RO film）.
Here with reference to Fig. 1, to possessing above-mentioned desalinization reverse osmosis membrane（RO film）Device for generating fresh water and possess
Above-mentioned regeneration water generating reverse osmosis membrane（RO film）Regeneration water generating device illustrate.
As shown in figure 1, device for generating fresh water 1 possesses：Fresh water generation turbidity removal film unit 11, has ultrafilter membrane（UF film）
Or micro-filtration membrane（MF film）, and filtration treatment is carried out to sea water A and obtains permeating water and condensed water B；Fresh water generates with a RO
Film unit 12, has reverse osmosis membrane（RO film）, and carried out with the infiltration water after turbidity removal film unit 11 to through this fresh water generation
Filtration treatment and obtain permeating water and condensed water B；And fresh water generates with the 2nd RO film unit 13, there is reverse osmosis membrane（RO
Film）, and to through this fresh water generate carry out filtration treatment with the infiltration water after a RO film unit 12 and obtain permeate water and
Condensed water B.
In addition, above-mentioned device for generating fresh water 1 is configured to：Sea water A is shifted to fresh water generation turbidity removal film unit 11,
Will transmit through the infiltration water after fresh water generation turbidity removal film unit 11 to be shifted with a RO film unit 12 to fresh water generation, will transmit through
Fresh water generates to be generated to fresh water with the infiltration water after a RO film unit 12 and is shifted with the 2nd RO film unit 13.In addition, it is above-mentioned light
Water generating device 1 is configured to：Condensed water B that each film unit being generated by fresh water is generated transfers to store condensed water groove
（Not shown）.And, above-mentioned device for generating fresh water 1 is configured to：Will transmit through above-mentioned fresh water to generate with after the 2nd RO film unit 13
Infiltration water as fresh water C reclaim.
Above-mentioned sea water A is the water of saliferous, is that for example salinity is the water of 1.0 ~ 8.0 mass %, more specifically, being salinity
Water for 2.5 ~ 6.0 mass %.
In this specification, sea water A is not limited in being present in marine water, as long as salinity is more than 1.0 mass %
Water, also includes lake water（Sabkha, brackish-water lake）, bog water, water etc. be present in the water on land.
As shown in figure 1, regeneration water generating device 2 possesses：Regeneration water generating turbidity removal film unit 21, has ultrafilter membrane
（UF film）Or micro-filtration membrane（MF film）, and filtration treatment is carried out to above-mentioned recycled treated water D, and obtain permeating water and condensed water E；With
And regeneration water generating RO film unit 22, there is reverse osmosis membrane（RO film）, and to through above-mentioned regeneration water generating turbidity removal film
Infiltration water after unit 21 carries out filtration treatment, and obtains permeating water and condensed water E.
In addition, above-mentioned regeneration water generating device 2 is configured to：By above-mentioned recycled treated water D to regeneration water generating turbidity removal
Shifted with film unit 21, will transmit through the infiltration water after regeneration water generating turbidity removal film unit 21 to regeneration water generating RO film list
Unit 22 transfer.In addition, above-mentioned regeneration water generating device 2 is configured to：Dense by generated by each film unit of regeneration water generating
Shrink E is to store condensed water groove（Not shown）Transfer.And, above-mentioned regeneration water generating device 2 is configured to：Will transmit through above-mentioned again
Unboiled water generates and is reclaimed as recycled water F with the infiltration water after RO film unit 22.
In the method for modifying of the seperation film of first embodiment, make because for fresh water being carried out to sea water A using membrance separation
Change the reverse osmosis membrane causing the fresh water that separation function reduces to generate with a RO film unit 12 to obtain the fresh water C such as drinking water
（RO film）Contact with alkaline aqueous solution, thus to this reverse osmosis membrane（RO film）Micropore carry out expanding.And, first embodiment
Seperation film method of modifying pass through to this reverse osmosis membrane（RO film）Micropore carry out expanding, thus obtain regenerate water generating RO
The reverse osmosis membrane of film unit 22（RO film）.
Above-mentioned fresh water generates and is formed by cellulose acetate with the reverse osmosis membrane of a RO film unit 12.In above-mentioned acetate fiber
In element, the quantity of the acetyl group containing in glucose unit is not particularly limited, but for example exemplified with 1 ~ 3, degree of acetylation is preferred
For 50 ~ 70%, more preferably about 61%.
Here, degree of acetylation refers to the combination acetic acid amount of per unit weight cellulose acetate, ASTM：D-817-91（Acetic acid
The test method of cellulose etc.）The middle measurement according to degree of acetylation and calculating and the value tried to achieve.
In addition, above-mentioned fresh water generates the reverse osmosis membrane with a RO film unit 12（RO film）It is tens of for example formed as diameter
μm ~ film of the thread type being referred to as hollow fiber membrane of hollow of number mm.
The pH of above-mentioned alkaline aqueous solution is 10 ~ 13, preferably 11 ~ 13, more preferably 12 ~ 13.
Can include as above-mentioned alkaline aqueous solution, for example sodium hydrate aqueous solution, calcium hydroxide aqueous solution, ammonia is molten
Liquid etc..
The method of modifying of the seperation film of first embodiment, is generated with a RO film list from fresh water by making alkaline aqueous solution
The supply mouth for feedwater of unit 12 flows into, and so that alkaline aqueous solution is contacted with separation membrane surface in non-transmission mode, thus to light
The water generating reverse osmosis membrane of the first RO film unit 12（RO film）Micropore carry out expanding.In addition, alkaline aqueous solution is given birth to fresh water
Become to be generated from fresh water with the supply of a RO film unit 12 and carried out with the concentration water out of a RO film unit.
For the method for modifying of the seperation film of first embodiment, in the alkaline aqueous solution for 11 ~ 13 using pH, and pass through
Above-mentioned contact fresh water is generated with the reverse osmosis membrane with a RO film unit 12（RO film）Pore carry out in expanding mode, with
Preferably 20 ~ 100 hours time of contact of alkaline aqueous solution, more preferably 20 ~ 50 hours.
The method of modifying of the seperation film of first embodiment is constituted as described above, the modification of the seperation film of first embodiment
Device is configured to by making to be contacted with alkaline aqueous solution by the seperation film that cellulose acetate is formed, thus micro- to this seperation film
Hole carries out expanding.
In addition, though the reforming apparatus of the method for modifying of the seperation film of first embodiment and seperation film have above-mentioned knot
Structure, but the reforming apparatus of the method for modifying of the seperation film of the present invention and seperation film are not limited to said structure, can suitably enter
Row design alteration.
For example, the method for modifying of the seperation film of first embodiment is to reverse osmosis membrane（RO film）Micropore carry out expanding,
Can also be to ultrafilter membrane（UF film）, micro-filtration membrane（MF film）Carry out expanding etc. the micropore of seperation film.In addition, reverse osmosis membrane includes nanofiltration
Film（NF film）.
In addition, though in the method for modifying of the seperation film of first embodiment, to the type being referred to as hollow fiber membrane
The micropore of film carry out expanding, but it is also possible to having than above-mentioned hollow fiber membrane in the method for modifying of the seperation film of the present invention
Diameter slightly count cm about the film of the type being referred to as tubular film of rugosity or when using to be internally provided with net etc.
The state of timbering material be wound in the envelope shape of web-like use the micropore being referred to as the known seperation film such as rolled film carry out expanding.
And although in the seperation film method of modifying of first embodiment, make because for being entered to sea water A using membrance separation
Row desalination causes the seperation film that separation function reduces to obtain the fresh water C such as drinking water（Specifically, fresh water generates and uses first
The reverse osmosis membrane of RO film unit 12（RO film））Micropore carry out expanding, but the method for modifying of the seperation film of the present invention can also
To the seperation film causing separation function to reduce because of various uses such as the purified treatment for waste water, employ specified time limit（Example
As the several years）Seperation film micropore carry out expanding.
In addition, though in the method for modifying of the seperation film of first embodiment, by above-mentioned expanding preparing for right
Above-mentioned recycled treated water D carries out membrance separation to obtain the regeneration water generating reverse osmosis membrane of recycled water F（RO film）（Regeneration water generating
Reverse osmosis membrane with RO film unit 22（RO film））, but in the method for modifying of the seperation film of the present invention, as long as can use micro-
The diameter in hole is than micropore by expanding seperation film（Micropore diameter）The purposes of big seperation film, can be modified to for other
The seperation film of purposes.In addition, however it is not limited to reverse osmosis membrane in the method for modifying of the seperation film of the present invention, as long as micropore
Diameter is than micropore by expanding seperation film（Micropore diameter）Big seperation film, then can also be modified to ultrafilter membrane（UF film）、
Micro-filtration membrane（MF film）Etc. seperation film.In addition, reverse osmosis membrane（RO film）Including NF membrane（NF film）.
And, the rate of change of the NaCl salt rejection rate of method of modifying preferable separate film of the seperation film of first embodiment is big
In 0% and for less than 70%, more preferably higher than 0% and be less than 50%.
In addition, the rate of change of NaCl salt rejection rate refers to the value being expressed from the next.Alternatively, it is also possible to replace NaCl with NaOH.
The rate of change of NaCl salt rejection rate（%）=[（The NaCl salt rejection rate of expanding front seperation film（%）- expanding after seperation film
NaCl salt rejection rate（%））The NaCl salt rejection rate of/expanding front seperation film（%）]×100
Second embodiment
Then, the reforming apparatus of the method for modifying to the seperation film of second embodiment and seperation film illustrate.
The present inventor is studied with keen determination, it was found that by making the seperation film being formed by cellulose acetate
Contact with alkaline aqueous solution to carry out expanding such that it is able to not only suppress the deterioration of this seperation film but also short to the micropore of this seperation film
In time, this seperation film is carried out expanding.According to this method, the ester bond of the acetyl group of cellulose acetate is by alkaline aqueous solution water
Solution, expanding therefore, it is possible to carry out to the micropore of the seperation film being formed by cellulose acetate.In addition, according to this method, with oxidation
Difference, because hydrolysis hardly causes damage to seperation film, therefore seperation film is not easily deteriorated.
However, for according to this method by expanding become need diameter seperation film, when with regulation pressure to this point
From mould send processed water when, compare by the seperation film after expanding, do not obtain sufficiently high flux, therefore, required in order to obtain
Flux must be with higher pressure to seperation film force feed processed water.That is, seperation film after expanding for this, exists and is difficult to high energy
Effect ground carries out the problem of membrance separation to processed water.
In view of the above problems, second embodiment with provide one kind can at short notice to being formed by cellulose acetate and
Deterioration is compared less and by pore size and high energy efficiency processed water can be carried out with the seperation film of membrance separation carried out expanding separation
The reforming apparatus of the method for modifying of film and seperation film are problem.
The seperation film method of modifying of second embodiment, by making to be contacted with alcohol by the seperation film that cellulose acetate is formed,
Thus carry out expanding to the micropore of this seperation film.
In addition, in this manual, " modification of seperation film " refers to the expanding of the micropore of seperation film.By make seperation film with
Alcohol contact the micropore of this seperation film carried out expanding to contact with alcohol thus reducing seperation film by making seperation film
The mode of NaCl salt rejection rate is determining.The NaCl salt rejection rate of seperation film is to NaCl solution with seperation film（Raw water）Filtered and
Obtain filter liquor, measure the NaCl concentration of raw water and filter liquor, and the value that these measured values are brought into following formula and calculated.Separately
Outward, because NaCl concentration and electric conductivity are in line relation it is also possible to be replaced with mensure electric conductivity measuring NaCl concentration, Jin Erji
Calculate NaCl salt rejection rate.
NaCl salt rejection rate（%）=（1-Cp/Cf）×100
Cf：The NaCl concentration of raw water, Cp：The NaCl concentration of filter liquor
Specifically, the method for modifying of the seperation film of second embodiment is to because light for being carried out to sea water using membrance separation
Aquation causes the desalinization reverse osmosis membrane that separation function reduces to obtain the fresh water such as drinking water（RO film）Or employ
Specified time limit（The such as several years）Desalinization reverse osmosis membrane（RO film）Micropore carry out expanding.And, second embodiment
Seperation film method of modifying to this desalinization reverse osmosis membrane（RO film）Micropore carry out expanding, thus obtaining for profit
With active sludge treatment groove and equipment for separating liquid from solid, sewage is carried out with recycled treated water obtained from purified treatment and carry out membrance separation
And obtain the regeneration water generating reverse osmosis membrane of recycled water（RO film）.
In addition, regeneration water generating reverse osmosis membrane（RO film）With desalinization reverse osmosis membrane（RO film）Compare, do not require
Obtain high-purity infiltration water, but require to obtain the infiltration water of ormal weight compared with low dynamics, accordingly, as regeneration water generating reverse osmosis
Permeable membrane（RO film）, being usually used can be with than desalinization reverse osmosis membrane（RO film）The film that more low dynamics are filtered.Therefore,
To desalinization reverse osmosis membrane（RO film）Micropore carried out expanding reverse osmosis membrane（RO film）Can be suitable as regenerating
Water generating reverse osmosis membrane（RO film）.
Here with reference to Fig. 1, to possessing above-mentioned desalinization reverse osmosis membrane（RO film）Device for generating fresh water and possess
Above-mentioned regeneration water generating reverse osmosis membrane（RO film）Regeneration water generating device illustrate.
As shown in figure 1, device for generating fresh water 1 possesses：Fresh water generation turbidity removal film unit 11, has ultrafilter membrane（UF film）
Or micro-filtration membrane（MF film）, and filtration treatment is carried out to sea water A and obtains permeating water and condensed water B；Fresh water generates with a RO
Film unit 12, has reverse osmosis membrane（RO film）, and carried out with the infiltration water after turbidity removal film unit 11 to through this fresh water generation
Filtration treatment and obtain permeating water and condensed water B；And fresh water generates with the 2nd RO film unit 13, there is reverse osmosis membrane（RO
Film）, and to through this fresh water generate carry out filtration treatment with the infiltration water after a RO film unit 12 and obtain permeate water and
Condensed water B.
In addition, above-mentioned device for generating fresh water 1 is configured to：Sea water A is shifted to fresh water generation turbidity removal film unit 11,
Will transmit through the infiltration water after fresh water generation turbidity removal film unit 11 to be shifted with a RO film unit 12 to fresh water generation, will transmit through
Fresh water generates to be generated to fresh water with the infiltration water after a RO film unit 12 and is shifted with the 2nd RO film unit 13.In addition, it is above-mentioned light
Water generating device 1 is configured to：Condensed water B that each film unit being generated by fresh water is generated transfers to store condensed water groove
（Not shown）.And, above-mentioned device for generating fresh water 1 is configured to：Will transmit through above-mentioned fresh water to generate with after the 2nd RO film unit 13
Infiltration water as fresh water C reclaim.
Above-mentioned sea water A is the water of saliferous, is that for example salinity is the water of 1.0 ~ 8.0 mass %, more specifically, being salinity
Water for 2.5 ~ 6.0 mass %.
In this specification, sea water A is not limited in being present in marine water, as long as salinity is more than 1.0 mass %
Water, also includes lake water（Sabkha, brackish-water lake）, bog water, water etc. be present in the water on land.
As shown in figure 1, regeneration water generating device 2 possesses：Regeneration water generating turbidity removal film unit 21, has ultrafilter membrane
（UF film）Or micro-filtration membrane（MF film）, and filtration treatment is carried out to above-mentioned recycled treated water D, and obtain permeating water and condensed water E；With
And regeneration water generating RO film unit 22, there is reverse osmosis membrane（RO film）, and to through above-mentioned regeneration water generating turbidity removal film
Infiltration water after unit 21 carries out filtration treatment, and obtains permeating water and condensed water E.
In addition, above-mentioned regeneration water generating device 2 is configured to：By above-mentioned recycled treated water D to regeneration water generating turbidity removal
Shifted with film unit 21, will transmit through the infiltration water after regeneration water generating turbidity removal film unit 21 to regeneration water generating RO film list
Unit 22 transfer.In addition, above-mentioned regeneration water generating device 2 is configured to：Dense by generated by each film unit of regeneration water generating
Shrink E is to store condensed water groove（Not shown）Transfer.And, above-mentioned regeneration water generating device 2 is configured to：Will transmit through above-mentioned again
Unboiled water generates and is reclaimed as recycled water F with the infiltration water after RO film unit 22.
In the method for modifying of the seperation film of second embodiment, make because for fresh water being carried out to sea water A using membrance separation
Change the reverse osmosis membrane causing the fresh water that separation function reduces to generate with a RO film unit 12 to obtain the fresh water C such as drinking water
（RO film）Contact with alcohol-water solution, thus to this reverse osmosis membrane（RO film）Micropore carry out expanding.And, second embodiment
The method of modifying of seperation film passes through to this reverse osmosis membrane（RO film）Micropore carry out expanding, thus obtain regenerate water generating RO film
The reverse osmosis membrane of unit 22（RO film）.
Above-mentioned fresh water generates and is formed by cellulose acetate with the reverse osmosis membrane of a RO film unit 12.In above-mentioned acetate fiber
In element, the quantity of the acetyl group containing in glucose unit is not particularly limited, but for example exemplified with 1 ~ 3, degree of acetylation is preferred
For 50 ~ 70%, more preferably about 61%.
Here, degree of acetylation refers to the combination acetic acid amount of per unit weight cellulose acetate, ASTM：D-817-91（Acetic acid
The test method of cellulose etc.）The middle measurement according to degree of acetylation and calculating and the value tried to achieve.
In addition, above-mentioned fresh water generates the reverse osmosis membrane with a RO film unit 12（RO film）It is tens of for example formed as diameter
μm ~ film of the thread type being referred to as hollow fiber membrane of hollow of number mm.
As above-mentioned alcohol, such as methanol, ethanol, propanol etc. can be included.
The seperation film method of modifying of second embodiment, generates the supply with a RO film unit 12 by making alcohol from fresh water
The supply mouth of water flows into, and so that alcohol is contacted with separation membrane surface in non-transmission mode, thus generating fresh water with a RO film list
The reverse osmosis membrane of unit 12（RO film）Micropore carry out expanding.In addition, alcohol-water solution generates the confession with a RO film unit to fresh water
Carried out with the concentration water out of a RO film unit to generating from fresh water.
The method of modifying of the seperation film of second embodiment, preferably uses 10 ~ 90 volumes %, more preferred 40 ~ 60 volumes %
Alcohol-water solution, and above by contacting, fresh water is being generated with the reverse osmosis membrane of a RO membrane module 12（RO film）Micropore
Carry out in expanding mode, and be preferably set to 5 minutes ~ 100 hours the time of contact of alcohol-water solution, more preferably 10 minutes ~
50 hours.
The method of modifying of the seperation film of second embodiment is constituted as described above, the modification of the seperation film of second embodiment
Device is configured to by making to be contacted with alcohol by the seperation film that cellulose acetate is formed, thus expanding to the micropore of this seperation film
Footpath.
In addition, though the reforming apparatus of the method for modifying of the seperation film of second embodiment and seperation film have above-mentioned knot
Structure, but the reforming apparatus of the method for modifying of the seperation film of the present invention and seperation film are not limited to said structure, can suitably enter
Row design alteration.
For example, the method for modifying of the seperation film of second embodiment is to reverse osmosis membrane（RO film）Micropore carry out expanding,
Can also be to ultrafilter membrane（UF film）, micro-filtration membrane（MF film）Carry out expanding etc. the micropore of seperation film.In addition, reverse osmosis membrane includes nanofiltration
Film（NF film）.
In addition, though in the method for modifying of the seperation film of second embodiment, to the type being referred to as hollow fiber membrane
The micropore of film carry out expanding, but it is also possible to having than above-mentioned hollow fiber membrane in the method for modifying of the seperation film of the present invention
Diameter slightly count cm about the film of the type being referred to as tubular film of rugosity or when using to be internally provided with net etc.
The state of timbering material be wound in the envelope shape of web-like use the micropore being referred to as the known seperation film such as rolled film carry out expanding.
And although in the seperation film method of modifying of second embodiment, make because for being entered to sea water A using membrance separation
Row desalination causes the seperation film that separation function reduces to obtain the fresh water C such as drinking water（Specifically, fresh water generates and uses first
The reverse osmosis membrane of RO film unit 12（RO film））Micropore carry out expanding, but the method for modifying of the seperation film of the present invention can also
To the seperation film causing separation function to reduce because of various uses such as the purified treatment for waste water, employ specified time limit（Example
As the several years）Seperation film micropore carry out expanding.
In addition, though in the method for modifying of the seperation film of second embodiment, by above-mentioned expanding preparing for right
Above-mentioned recycled treated water D carries out membrance separation to obtain the regeneration water generating reverse osmosis membrane of recycled water F（RO film）（Regeneration water generating
Reverse osmosis membrane with RO film unit 22（RO film））, but in the method for modifying of the seperation film of the present invention, as long as can use micro-
The diameter in hole is than micropore by expanding seperation film（Micropore diameter）The purposes of big seperation film, can be modified to for other
The seperation film of purposes.In addition, however it is not limited to reverse osmosis membrane in the method for modifying of the seperation film of the present invention, as long as micropore
Diameter is than micropore by expanding seperation film（Micropore diameter）Big seperation film, then can also be modified to ultrafilter membrane（UF film）、
Micro-filtration membrane（MF film）Etc. seperation film.In addition, reverse osmosis membrane（RO film）Including NF membrane（NF film）.
And, the rate of change of the NaCl salt rejection rate of method of modifying preferable separate film of the seperation film of second embodiment is big
In 0% and for less than 90%, more preferably higher than 0% and be less than 80%.
In addition, the rate of change of NaCl salt rejection rate refers to the value being expressed from the next.
The rate of change of NaCl salt rejection rate（%）=[（The NaCl salt rejection rate of expanding front seperation film（%）- expanding after seperation film
NaCl salt rejection rate（%））The NaCl salt rejection rate of/expanding front seperation film（%）]×100
Embodiment
Then, enumerate 1 to 3 couple of present invention of test to be further described in detail.
（Test 1：Alkaline aqueous solution and acidic aqueous solution, high-temperature water and the comparison containing aqueous oxidizing agent solution）
（Example 1-1：Alkaline aqueous solution）
By from having the reverse osmosis membrane being formed by cellulose acetate（RO film）RO film unit（Japan's textile company system, business
The name of an article：ホロセップ（HB10255FI））The hollow-fibre membrane cutting out impregnated in alkaline aqueous solution（The sodium hydroxide of PH13
Aqueous solution）So as to contact time of contact according to table 1.In addition, in following table 0 hour time of contact refer to reverse osmosis membrane（RO film）
The meaning not contacted with alkaline aqueous solution（0 hour time of contact in example 3 was also same case）.
Then, the reverse osmosis membrane after contacting with alkaline aqueous solution time of contact table 1 being pressed to each（RO film）Apply table 1 institute
The pressure showing（Intermembranous pressure reduction）, from RO film unit is filtered with distributary for the supply mouth feeding water, the flow of condensed water is as 1L/min
Mode supply pure water, the amount measuring infiltration water reaches the time till 25mL（Time of penetration）.Result is shown in table 1.
[table 1]
※ represents more than 60 minutes.
（Example 1-2：Acidic aqueous solution）
Except using acidic aqueous solution（5 mass % aqueous sulfuric acids）Replace alkaline aqueous solution and institute's time of contact such as table 2
Beyond showing, to make acidic aqueous solution and reverse osmosis membrane with example 1-1 identical method（RO film）Contact, then with identical with example 1-1
Method measure pure water time of penetration.Result is shown in table 2.
[table 2]
（Example 1-3：High-temperature water）
Except using tap water replace alkaline aqueous solution, and by this tap water keep 90 DEG C in the state of make seperation film with
90 DEG C of tap water（High-temperature water）Contact, and beyond time of contact is as shown in table 3, to make high temperature with example 1-1 identical method
Water and reverse osmosis membrane（RO film）Contact, then to measure the time of penetration of pure water with example 1-1 identical method.Result is shown in table 3.
[table 3]
（Example 1-4：Containing aqueous oxidizing agent solution）
Except using containing aqueous oxidizing agent solution（The hypochlorous aqueous solution of 200ppm）Replace alkaline aqueous solution, and during contact
Between as shown in table 4 beyond, to make containing aqueous oxidizing agent solution and reverse osmosis membrane with example 1-1 identical method（RO film）Contact, then
To measure the time of penetration of pure water with example 1-1 identical method.Result is shown in table 4.
[table 4]
As shown in table 1 to 4, show when using alkaline aqueous solution, with using high-temperature water, acidic aqueous solution, contain oxidant
The situation of aqueous solution is compared, and can shorten the time of penetration of the seperation film being formed by cellulose acetate, that is, can be to seperation film
Micropore carries out expanding.
In addition, it is believed that 3 hours afterwards still being enlarged aperture when using alkaline aqueous solution, but it is believed that material
Intensity decreases, be difficult to due to pressure keep macaroni yarn shape, runner block.
（Test 2：Alkaline aqueous solution and the comparison of alcohol-water solution）
（Example 2-1：Alkaline aqueous solution, time of contact：48h）
Using 180 from having the reverse osmosis membrane being formed by Triafol T（RO film）RO film unit（Japan weaves
Company system, trade name：ホロセップ（HB10255FI））The hollow fiber membrane cutting out is prepared into small-sized RO membrane module.Make alkalescence
Aqueous solution（pH：12.7, electric conductivity：The NaOH aqueous solution of 5mS/cm）Flow into for the supply mouth of feedwater from small-sized RO membrane module,
Alkaline aqueous solution and reverse osmosis membrane are made in non-transmission mode（RO film）Contact 48 hours.
Then, to modified reverse osmosis membrane（RO film）Apply the operating pressure of table 5（Intermembranous pressure reduction）, from RO membrane module
Supply mouth for feedwater supplies pure water in the mode as 1L/min for the flow of condensed water in distributary filtration, gained in measurement 10 minutes
Infiltration water amount（Pure water Flux：Pure water flux）.
In addition, to before modified and modified reverse osmosis membrane（RO film）Apply the operating pressure of table 5（Intermembranous pressure reduction）, from RO
The mode with the flow of condensed water in distributary filtration as 1L/min for the supply mouth for feedwater of film unit supplies NaCl aqueous solution
（NaCl concentration：6 mass %）, measure the amount of the infiltration water of gained in 10 minutes（NaCl-Flux：NaCl flux）.In addition, also surveying
Measure the electric conductivity as the NaCl aqueous solution for feedwater（NaCl electric conductivity）Electric conductivity with infiltration water.
In addition, similarly, with modified reverse osmosis membrane（RO film）Identical, to reverse osmosis membrane before modified（RO film）Also enter
Row identical measures.
This test is repeated 3 times.Result is shown in table 5.In addition, pure water flux（Flux）Increment rate represents modified
Reverse osmosis membrane（RO film）Pure water flux and reverse osmosis membrane before modified（RO film）Pure water flux ratio.Also phase in other tables
With.
[table 5]
（Example 2-2：Alcohol-water solution, time of contact：20min）
Except using alcohol-water solution（50 volume % ethanol waters）Replace alkaline aqueous solution, and be changed to time of contact
Beyond 20min, to be tested with example 2-1 identical method.Result is shown in table 6.
[table 6]
（Example 2-3：Alcohol-water solution, time of contact：24h）
In addition to being changed to 24h time of contact, to be tested with example 2-2 identical method.Result is shown in table 7.
[table 7]
As shown in table 5, it is modified with 48 hour time of contact by using alkaline aqueous solution, pure water flux increment rate is put down
It is 1.3 times, the rate of change average out to 37.1% of NaCl salt rejection rate.On the other hand, enter within 24 hours by using alcohol-water solution contact
Row is modified, 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.It is indicated above that using
The modification of alcohol-water solution compared with the modification employing alkaline aqueous solution, compare by size can high energy efficiency to processed water
Carry out membrance separation.
It is also shown that employing the modification of alcohol-water solution as the modification employing alkaline aqueous solution, can shorten by vinegar
The time of penetration of the seperation film that acid cellulose is formed, can carry out expanding to the micropore of seperation film.
And, for employing the modification of alcohol-water solution, identical with the modification employing alkaline aqueous solution, all do not observe
The deterioration of the seperation film being formed by cellulose acetate.
（Test 3）
Except using NaOH aqueous solution（pH：12.7, electric conductivity：5mS/cm）Replace NaCl aqueous solution, and modification time
Beyond as shown in table 8, for the modification based on alkaline aqueous solution, carry out and test the test phase in 2, NaCl aqueous solution being carried out
Same test.
This test is repeated 3 times.Result is shown in table 8.
[table 8]
Show as shown in table 8, modification time longer Development of Modification degree is bigger.
Symbol description
1：Device for generating fresh water, 2：Regeneration water generating device
11：Fresh water generation turbidity removal film unit, 12：Fresh water generates with a RO film unit
13：Fresh water generate with the 2nd RO film unit, 21：Regeneration water generating turbidity removal film unit
22：Regeneration water generating RO film unit, A：Sea water
B：Condensed water, C：Fresh water, D：Recycled treated water
E：Condensed water, F：Recycled water
Claims (2)
1. a kind of method of modifying of seperation film it is characterised in that
By making to be formed by cellulose acetate, for desalinization being obtained fresh water by membrance separation, separation function have dropped
Desalinization seperation film contact 20 to 100 hours with alkaline aqueous solution, thus carry out expanding to the micropore of this seperation film, obtain
Water generating seperation film must be regenerated.
2. a kind of method of modifying of seperation film it is characterised in that
By making to be formed by cellulose acetate, for desalinization being obtained fresh water by membrance separation, separation function have dropped
Desalinization seperation film contact with alcohol so that this seperation film NaCl salt rejection rate reduce, obtain regeneration water generating with point
From film.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010039877A JP5222869B2 (en) | 2010-02-25 | 2010-02-25 | Separation membrane reforming method and separation membrane reforming apparatus |
| JP2010-039877 | 2010-02-25 | ||
| JP2010098695A JP5222886B2 (en) | 2010-04-22 | 2010-04-22 | Separation membrane reforming method and separation membrane reforming apparatus |
| JP2010-098695 | 2010-04-22 | ||
| PCT/JP2011/052312 WO2011105188A1 (en) | 2010-02-25 | 2011-02-04 | Separation membrane modification method and separation membrane modification device |
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| Publication Number | Publication Date |
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| CN102753255A CN102753255A (en) | 2012-10-24 |
| CN102753255B true CN102753255B (en) | 2017-02-08 |
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| WO (1) | WO2011105188A1 (en) |
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| CN109200615B (en) * | 2017-06-30 | 2021-10-08 | 中国石油化工股份有限公司 | Treatment method of tail gas produced in hydrogen peroxide preparation process |
| CN109200772B (en) * | 2017-06-30 | 2021-10-08 | 中国石油化工股份有限公司 | Method for treating tail gas in process of preparing maleic anhydride from butane |
| 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 |
| 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 |
| CN112452161B (en) * | 2020-11-26 | 2021-09-21 | 四川大学 | Hydrophilic membrane and preparation method thereof |
| CN113461109B (en) * | 2021-08-02 | 2022-07-26 | 广东工业大学 | Multistage reverse osmosis process and system capable of regulating and controlling desalination rate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101524624A (en) * | 2008-09-09 | 2009-09-09 | 上海立源水处理技术有限责任公司 | Gas drive membrane separation method and membrane separation device |
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| JPS61107921A (en) * | 1984-11-01 | 1986-05-26 | Asahi Chem Ind Co Ltd | Manufacture of composite hollow yarn membrane |
| JPH0531337A (en) * | 1991-07-31 | 1993-02-09 | Asahi Chem Ind Co Ltd | Method for making hollow yarn ultrafiltration membrane hydrophilic |
| US20040206693A1 (en) * | 2003-04-16 | 2004-10-21 | John Charkoudian | Crosslinked cellulosic membrane |
| JP4177231B2 (en) * | 2003-11-04 | 2008-11-05 | 日東電工株式会社 | Liquid separation membrane and method for producing the same |
| JP4675062B2 (en) * | 2004-06-07 | 2011-04-20 | 旭化成ケミカルズ株式会社 | Hollow fiber membrane cartridge |
| JP2006083292A (en) * | 2004-09-16 | 2006-03-30 | Fuji Photo Film Co Ltd | Method for stably producing microporous membrane and use thereof in method for separating and purifying nucleic acid |
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2011
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| CN101524624A (en) * | 2008-09-09 | 2009-09-09 | 上海立源水处理技术有限责任公司 | Gas drive membrane separation method and membrane separation device |
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