CN107224875A - A kind of processing method of reverse osmosis membrane - Google Patents

A kind of processing method of reverse osmosis membrane Download PDF

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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
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Pending
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CN201710657464.3A
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Chinese (zh)
Inventor
何浩明
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Individual
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Individual
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Priority to CN201710657464.3A priority Critical patent/CN107224875A/en
Publication of CN107224875A publication Critical patent/CN107224875A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025Reverse osmosis; Hyperfiltration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081After-treatment of organic or inorganic membranes
    • B01D67/0093Chemical modification
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment 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

A kind of processing method of reverse osmosis membrane
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.
CN201710657464.3A 2017-08-03 2017-08-03 A kind of processing method of reverse osmosis membrane Pending CN107224875A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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