CN107224875A - A kind of processing method of reverse osmosis membrane - Google Patents
A kind of processing method of reverse osmosis membrane Download PDFInfo
- Publication number
- CN107224875A CN107224875A CN201710657464.3A CN201710657464A CN107224875A CN 107224875 A CN107224875 A CN 107224875A CN 201710657464 A CN201710657464 A CN 201710657464A CN 107224875 A CN107224875 A CN 107224875A
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- CN
- China
- Prior art keywords
- reverse osmosis
- osmosis membrane
- fluorination
- mixed gas
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D67/0093—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
Abstract
A kind of processing method of reverse osmosis membrane, described process chamber is equipped for carrying heater, is connected with the nitrogen pipeline with control device and fluorine nitrogen mixed gas pipeline, and directly reverse osmosis membrane is placed in fluorination room during processing, the pre-heat treatment dehydration is first carried out before fluorination;It is passed through after nitrogen emptying air, then fluorine nitrogen mixed gas is passed through by fluorination treatment room by valve and reverse osmosis membrane is fluorinated, at ambient pressure, fluorine gas is 1% 5% in the concentration of fluorine nitrogen mixed gas.The temperature of fluorination process, pressure can be adjusted, and realization is automatically controlled, and increase the security of fluorination process and the controllability of degree of fluorination.Material for reverse osmosis membrane processing is more, mainly there is a variety of complex reverse osmosis membranes of class such as modified aromatic polyamide complex reverse osmosis membrane, modified PVDF reverse osmosis membranes, modified acetate fiber complex reverse osmosis membrane.More bright and clean fluorinated material layer is formed by handling anti-permeable membrane surface, membrane micropore is reduced and gradually blocks, improve the service efficiency of film.
Description
Technical field
The present invention relates to a kind of processing method of reverse osmosis membrane, belong to environmental technology field.
Background technology
Water is lifespring, and it has important effect to industry, agricultural, developing for business.But past several
In 10 years, the change of weather and the irrational utilization of water etc. cause the fresh water total amount that can directly use fewer and fewer, water money
The problem of source is short has turned into the hot issue that the 21 century mankind are concerned about.Reverse osmosis technology is considered as that solution freshwater resources are short
A kind of scarce effective way, has the advantages that cost is relatively low, desalting efficiency is high, is widely used in seawater/brackish water desalination, life
All many-sides such as thing, medicine, food.Reverse osmosis membrane is mostly important part in counter-infiltration system, and its performance difference is direct
Determine the performance quality of counter-infiltration system.From nano-angle, reverse osmosis membrane is non-smooth finish surface, easy quilt during use
Organogenous sediment(Such as various microorganisms, bacterium algae)And inorganic sediment(Such as calcium sulfate and calcium carbonate, magnesium)Attachment, makes film micro-
Hole is gradually blocked, and causes disposal ability to decline, it is necessary to which periodic cleaning, causes processing cost to increase.
The present invention intends proposing that one kind, to commercialized reverse osmosis membrane fluorine gas fluorination treatment method, increases the surface of reverse osmosis membrane
Finish, reduces absorption of the pollution on film surface, extends replacing construction cycle and the increase reverse osmosis membrane service life of film.
The content of the invention
It is an object of the invention to provide a kind of method of new processing reverse osmosis membrane, the performance of reverse osmosis membrane can be improved, increased
Plus reverse osmosis membrane service life.
A kind of processing method of reverse osmosis membrane of the present invention, described equipment and main process, including following part:
(1)Main device structure is:For reverse osmosis membrane fluorination treatment room, with heater, fluorination treatment room is connected with band control
The nitrogen pipeline and fluorine nitrogen mixed gas pipeline of device processed.
(2)Directly reverse osmosis membrane is placed in fluorination room, the pre-heat treatment dehydration, dehydration temperaturre 150 are first carried out before fluorination
DEG C, dewatering time 3-5 hours, to remove the free water and the crystallization water in reverse osmosis membrane, temperature range is at 50 DEG C to 200 DEG C.
(3)After the completion of dehydration, it is passed through after nitrogen emptying air, then fluorine nitrogen mixed gas is passed through by fluorination treatment by valve
Room is fluorinated to reverse osmosis membrane, at ambient pressure, and fluorine gas is 1%-5% in the concentration of fluorine nitrogen mixed gas.
(4)The temperature of fluorination process can be adjusted, adjustable range:From 0 DEG C to 200 DEG C, fluorination chamber pressure can also be adjusted
Section, adjustable range:Pressure can be pressurized from 0.1MPa to 1MPa.
The device is realized and automatically controlled, and increases the security of fluorination process and the controllability of degree of fluorination.
(5)Material for reverse osmosis membrane is more, mainly there is modified aromatic polyamide complex reverse osmosis membrane, modified PVDF
The a variety of complex reverse osmosis membranes of class such as reverse osmosis membrane, modified acetate fiber complex reverse osmosis membrane.
A kind of processing method of above-mentioned reverse osmosis membrane, wherein, processing scheme preferably is as follows:
(1)150 DEG C of dehydration temperaturre, dewatering time 3 hours.
(2)The concentration 1% of fluorine nitrogen mixed gas, the pressure 0.5MPa of fluorine nitrogen mixed gas are filled with during fluorination.
(3)It is fluorinated temperature 50 C, 3 hours processing times.
(4)The reverse osmosis membrane used mainly have modified aromatic polyamide complex reverse osmosis membrane, modified PVDF reverse osmosis membranes,
Modified acetate fiber complex reverse osmosis membrane.
The present invention principle be:
Pretreatment of the complex reverse osmosis membrane through overheat removes free moisture, and being handled through hyperthermia makes the dehydration formation such as hydroxyl or amido
Double bond, then fluorine gas enters to exchange generation C-F keys or fluorine gas with the hydrogen on reverse osmosis membrane surface and double bond addition forms C-F keys,
More bright and clean fluorinated material layer is so formed on film surface, organic and inorganic sediment is difficult, in film surface attachment, to reduce film
Micropore is gradually blocked, and improves the service efficiency of film.C h bond is replaced with C-F keys simultaneously, makes the chemical stability of film and anti-oxidant
Ability is strengthened, therefore extends the service life of film.
Brief description of the drawings
Fig. 1 is fluorination treatment room schematic diagram.
Wherein:1 is fluorination treatment room;2 be to connect vacuum system;3 be nitridation pipeline;4 be fluorine nitrogen mixed gas pipeline;5 be to treat
Handle diaphragm.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The preparation of modified aromatic polyamide complex reverse osmosis membrane.First, commercial aromatic polyamide membrane is hung in fluorination room, often
Temperature is evacuated to -0.098MPa, and maintains about 5 minutes, is re-filled with nitrogen to normal pressure;Be warming up to 50 DEG C be evacuated to again-
0.098MPa, and maintain about 5 minutes, nitrogen is re-filled with to normal pressure;Then 150 DEG C are warming up to and is evacuated to -0.098MPa, is maintained
1 hour;Then 50 DEG C are cooled under vacuumized conditions, 1% fluorine nitrogen mixed gas is slowly introducing and fluorine is carried out to film to pressure 0.5MPa
Change is handled.The process of fluorination reaction is determined by the change of pressure, treats that gauge hand stablizes 10 minutes without the reduction of obvious pressure
When represent that fluorination reaction terminates, be fluorinated about 3 hours time.- 0.098MPa is evacuated to, and maintains vacuum cooled to normal temperature, is filled
Enter nitrogen to normal pressure.Take out, be assembled into membrane module to be tested.
The processing water contrast of the embodiment 1 of table 1
Project | Effluent quality electrical conductivity | Salt rejection rate | (25 DEG C of aquifer yield/H) | Replacement cycle | Service life |
Embodiment 1 | Less than 5us/cm | 98% | 15 tons | 14 days | 36 months |
It is untreated | Less than 15us/cm | 95% | 12 tons | 7 days | 18 months |
Embodiment 2
The preparation of modified PVDF counter-infiltrations film again.First, commercial pvdf membrane being hung in fluorination room, normal temperature is evacuated to-
0.098MPa, and maintain about 5 minutes, nitrogen is filled with to normal pressure;It is warming up to 50 DEG C and is evacuated to -0.098MPa again, and maintains about 5
Minute, nitrogen is re-filled with to normal pressure;Then 200 DEG C are warming up to and is evacuated to -0.098MPa, is maintained 1 hour;Then vacuumizing
Under the conditions of be cooled to 50 DEG C, be slowly introducing % fluorine nitrogen mixed gas to pressure 0.5MPa to film carry out fluorination treatment.Fluorination reaction is entered
The change that journey leads to excess pressure is determined, represents that fluorination reaction terminates when gauge hand is stablized and reduced without obvious pressure for 10 minutes,
About 3 hours fluorination time.- 0.098MPa is evacuated to after the completion of fluorination, and maintains vacuum cooled to normal temperature, nitrogen is filled with to normal
Pressure.Take out, be assembled into membrane module to be tested.
The processing water contrast of the embodiment 2 of table 2
Project | Effluent quality electrical conductivity | Salt rejection rate | (25 DEG C of aquifer yield/H) | Replacement cycle | Service life |
Embodiment 2 | Less than 5us/cm | 98% | 14 tons | 45 days | 40 months |
It is untreated | Less than 8us/cm | 97% | 12 tons | 15 days | 21 months |
Embodiment 3
Commercial acetate fiber complex reverse osmosis membrane first, is hung on fluorination by the preparation of modified acetate fiber complex reverse osmosis membrane
In room, normal temperature is evacuated to -0.098MPa, and maintains about 5 minutes, is re-filled with nitrogen to normal pressure;50 DEG C are warming up to vacuumize again
To -0.098MPa, and maintain about 5 minutes, be re-filled with nitrogen to normal pressure;Then 175 DEG C are warming up to and is evacuated to -0.098MPa,
Maintain 1 hour;Then 50 DEG C are cooled under vacuumized conditions, % fluorine nitrogen mixed gas is slowly introducing and film is entered to pressure 0.1MPa
Row fluorination treatment.The process of fluorination reaction is determined by the change of pressure, treats that gauge hand stablizes 10 minutes without obvious pressure
Represent that fluorination reaction terminates during reduction, be fluorinated about 3 hours time.- 0.098MPa is evacuated to after the completion of fluorination, and maintains vacuum
Normal temperature is cooled to, nitrogen is filled with to normal pressure.Take out, be assembled into membrane module to be tested.
The processing water contrast of the embodiment 3 of table 3
Project | Effluent quality electrical conductivity | Salt rejection rate | (25 DEG C of aquifer yield/H) | Replacement cycle | Service life |
Embodiment 3 | Less than 8us/cm | 95% | 18 tons | 15 days | 24 months |
It is untreated | Less than 14us/cm | 92% | 15 tons | 8 days | 15 months |
The processing cost of the film of table 4 fluorination is calculated(Every 10000 squares of surface areas)
Cost type | Material name | Consumption(Kilogram) | Cost(Member/KG) | Totle drilling cost(Member) |
Cost of material | Fluorine gas | 60 | 25 | 1500 |
Nitrogen | 46 | 1 | 37 | |
Power cost | 1500 | |||
Packing cost | 100 | |||
Human cost | 9 | 150 | 1350 | |
Total cost of production | 4487 |
From table 1-4, substantially, processing cost is not also high, has a extensive future for effect of the present invention.
Claims (2)
1. a kind of processing method of reverse osmosis membrane, it is characterized in that described equipment and main process, including following part:
Main device structure is:For reverse osmosis membrane fluorination treatment room, with heater, fluorination treatment room is connected with band control dress
The nitrogen pipeline and fluorine nitrogen mixed gas pipeline put;
Directly reverse osmosis membrane is placed in fluorination room, the pre-heat treatment dehydration, 150 DEG C of dehydration temperaturre, dehydration are first carried out before fluorination
Time 3-5 hour, to remove the free water and the crystallization water in reverse osmosis membrane, temperature range is at 50 DEG C to 200 DEG C;
After the completion of dehydration, it is passed through after nitrogen emptying air, then fluorine nitrogen mixed gas is passed through to reverse osmosis by fluorination treatment room by valve
Permeable membrane is fluorinated, at ambient pressure, and fluorine gas is 1%-5% in the concentration of fluorine nitrogen mixed gas;
The temperature of fluorination process can be adjusted, adjustable range:From 0 DEG C to 200 DEG C, fluorination chamber pressure can also be adjusted, and adjust model
Enclose:Pressure can be pressurized from 0.1MPa to 1MPa;
The device is realized and automatically controlled, and increases the security of fluorination process and the controllability of degree of fluorination;
Material for reverse osmosis membrane is more, mainly have modified aromatic polyamide complex reverse osmosis membrane, modified PVDF reverse osmosis membranes,
Modified acetate fiber complex reverse osmosis membrane class complex reverse osmosis membrane.
2. the processing method of a kind of reverse osmosis membrane according to claim 1, it is characterized in that described preferred process scheme is:
(1)150 DEG C of dehydration temperaturre, dewatering time 3 hours;
(2)The concentration 1% of fluorine nitrogen mixed gas, the pressure 0.5MPa of fluorine nitrogen mixed gas are filled with during fluorination;
(3)It is fluorinated temperature 50 C, 3 hours processing times;
(4)The reverse osmosis membrane used has modified aromatic polyamide complex reverse osmosis membrane, modified PVDF reverse osmosis membranes, modified acetic acid
Fiber composite reverse osmosis membrane.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111741804A (en) * | 2018-02-20 | 2020-10-02 | 吉尔松有限合伙公司 | Method for fluorinating a filter for a pipette tip, associated manufacturing method and pipette |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101880401A (en) * | 2010-06-24 | 2010-11-10 | 洛阳森蓝化工材料科技有限公司 | Polymer surface fluorination technique |
CN103328080A (en) * | 2011-06-17 | 2013-09-25 | Lg化学株式会社 | Reverse-osmosis membrane having an ultra-hydrophilic protective layer and method for producing same |
WO2015079442A1 (en) * | 2013-11-28 | 2015-06-04 | B. G. Negev Technologies And Applications Ltd | Fabrication and modification of polymer membranes using ink-jet printing |
CN106972139A (en) * | 2017-03-10 | 2017-07-21 | 深圳中兴创新材料技术有限公司 | A kind of hydrophilically modified method and device of MIcroporous polyolefin film |
-
2017
- 2017-08-03 CN CN201710657464.3A patent/CN107224875A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101880401A (en) * | 2010-06-24 | 2010-11-10 | 洛阳森蓝化工材料科技有限公司 | Polymer surface fluorination technique |
CN103328080A (en) * | 2011-06-17 | 2013-09-25 | Lg化学株式会社 | Reverse-osmosis membrane having an ultra-hydrophilic protective layer and method for producing same |
WO2015079442A1 (en) * | 2013-11-28 | 2015-06-04 | B. G. Negev Technologies And Applications Ltd | Fabrication and modification of polymer membranes using ink-jet printing |
CN106972139A (en) * | 2017-03-10 | 2017-07-21 | 深圳中兴创新材料技术有限公司 | A kind of hydrophilically modified method and device of MIcroporous polyolefin film |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111741804A (en) * | 2018-02-20 | 2020-10-02 | 吉尔松有限合伙公司 | Method for fluorinating a filter for a pipette tip, associated manufacturing method and pipette |
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Application publication date: 20171003 |