CN106957089A - A kind of twice-modified method of discarded reverse osmosis membrane available for treatment of dyeing wastewater - Google Patents
A kind of twice-modified method of discarded reverse osmosis membrane available for treatment of dyeing wastewater Download PDFInfo
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- CN106957089A CN106957089A CN201710248136.8A CN201710248136A CN106957089A CN 106957089 A CN106957089 A CN 106957089A CN 201710248136 A CN201710248136 A CN 201710248136A CN 106957089 A CN106957089 A CN 106957089A
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Classifications
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- 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
-
- 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
- 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
- B01D65/025—Removal of membrane elements before washing
-
- 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
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The present invention relates to a kind of twice-modified method of the discarded reverse osmosis membrane available for treatment of dyeing wastewater, the reverse osmosis membrane taken is not new film, but the reverse osmosis membrane discarded from other water treatment technologies, and secondary operation is carried out by the way of in situ or dystopy is modified to discarded reverse osmosis membrane（Cleaning, chemical treatment, surface second modification etc.）, promote waste and old reverse osmosis membrane flux and cutoff performance to recover.Described discarded reverse osmosis membrane is classified according to its stifled situation of pollution pollution before the use, and reasonably selects twice-modified mode according to the result of classification.Use cost of the reverse osmosis membrane in dyeing waste water is greatly reduced, is mainly shown as that the Costco Wholesale of film reduces 30 ~ 60%.The film of discarded counter-infiltration is subjected to secondary operation recycling, destruction of the discarded membrane module to environment can be greatly reduced.Discarded reverse osmosis membrane can not possibly return to original flux, but it still has preferable supporting layer, pervious bed etc., and still with larger value, the invention promotes the cycling and reutilization of resource.
Description
Technical field
The present invention relates to a kind of twice-modified method of the discarded reverse osmosis membrane available for treatment of dyeing wastewater, mainly include
Secondary operation is carried out by the way of in situ or dystopy is modified to discarded reverse osmosis membrane（Cleaning, chemical treatment, surface second
It is modified etc.）, promote waste and old reverse osmosis membrane flux and cutoff performance to recover, and it is useless in a certain actual printing and dyeing to demonstrate modified film
The effect in disposal process is handled in water.
Background technology
Printing and dyeing textile, as mainstay of the national economy industry, is on the one hand the pulling national economic development and promotion locality hundred
Surname employment is made that huge contribution, and a large amount of dyeing waste waters produced but then are also the important of China's industrial water pollution thing
Source.Dyeing waste water refers to the waste water of printing and dyeing mill's discharge based on processing cotton, fiber crops, chemical fibre and its blending product.It is often
Have the characteristics that：1）, waste water water is big, according to statistics per 1 ton of textile of dyeing and printing process will 100 ~ 200 tons of water consumption, wherein 80 ~
90% turns into waste water；2）, water-quality constituents is complicated and changeable, the noxious material (vulcanization added during sometimes with using various dyestuffs
Alkali, tartar emetic, aniline, copper sulphate, phenol etc.), it is alkalescence is presented more, and contain organic dyestuff, surfactant etc.；3）Colourity is very
Height, and SS is few, dyeing waste-water contains a variety of organic dyestuff (such as disperse dyes, direct dyes, acid dyes, azoic dyes, activity
Dyestuff, reducing dye etc.), colourity is high, and contains nitro and the heavy metal such as amine compound and chromium, zinc, arsenic in dye structure
Element, with larger bio-toxicity, it is difficult to degrade；4）Salt content is high in waste water, and this is primarily due to need in dyeing course
Substantial amounts of soda ash, sodium chloride or glauber salt (sodium sulphate) are added as accelerant and levelling agent, causes the salt content of waste water very
Height, the salt content of general dye vat draining seriously reduces the biodegradability of waste water up to 0.8 ~ 4%.Traditional dyeing waste water technique
The waste water of other production links such as dyeing waste-water and rinsing mixs, by the method diluted indirectly reduce the colourity of waste water with
Salt content, then pass through routine biochemistry --- materializing strategy technique carries out end-o f-pipe -control.Nonetheless, colourity and COD are still print
Contaminate the difficult point of wastewater to reach standard.China is the country of a serious water shortage again simultaneously, promotes dyeing to walk recycling economy hair
The road of exhibition.
In 2012, dyeing proposed more strict pollutant emission standard（GB4827-2012）, and require by
The reuse ratio of dyeing waste water is stepped up less than 10%, 12 during step raising printing-dying wastewater recycling ratio, such as 11th Five-Year
50% is up to 30%, 13 period.But the feature of the low profit of dyeing, makes it to select suitable dyeing waste water
Alap construction investment and operating cost are must take into consideration when processing disposal or reuse technology.Evaporation technique is to realize printing and dyeing
The effective technology of wastewater zero discharge, but evaporation process belongs to phase transition process, consumption quantity of steam or power consumption are very big, operating cost
It is high.Double membrane technologies（Milipore filter+reverse osmosis membrane）With relatively low operating cost, but it is limited to film and is easy to pollute and blocks, frequently
Backwash will cause the increase for running and changing film cost.In the actual treatment of dyeing waste water, even finding newly anti-
Permeable membrane, its in a short period of time flux also have very big decay, cause fouling membrane very serious, even if frequently anti-
Rinse and be also impossible to realize membrane flux 100% recovery.The technology of preparing of milipore filter is relatively ripe in China, the price of film
Also gradually reduce, but still there is larger gap, state with international most advanced level in terms of reverse osmosis membrane technology of preparing in China
Production film is difficult to play performance advantage, and the reverse osmosis membrane of high-quality still relies primarily on import, therefore reverse osmosis membrane would is that double film works
The key constraints of skill price and cost.For problem above, the present invention proposes by the use of discarded reverse osmosis membrane and is used as double films
Reverse osmosis membrane in method processing dyeing waste water, can greatly reduce and use film cost, and how to carry out correlation to discarded film and change
Property recover its filtering and cutoff performance be urgent need to resolve key issue.
The content of the invention
It is an object of the invention to provide a kind of cheap, reverse osmosis membrane available for treatment of dyeing wastewater twice-modified
Method.
In order to solve the above problems, main technical schemes of the invention are as follows：
The discarded reverse osmosis membrane assembly purchased is classified according to original purposes, drinking water deep purification film is such as applied to
Component, applied to the membrane module of industrial special wastewater treatment, applied to the membrane module of desalinization, according to the initial of reverse osmosis membrane
The indexs such as purposes, the flux of film of test carry out performance grade classification to discarded reverse osmosis membrane, and the film of different pollution levels will
Different processing mode and method of modifying is taken to recover.Specific classification situation and the twice-modified mode taken are as shown in table 1：
Table 1 discards the classification situation and modification mode selection list of reverse osmosis membrane
| Classification numbering | The initial use of former reverse osmosis membrane | Flux occupies percentage/% of original flux | Modification mode |
| 1 | Applied to drinking water deep purification（Comprising drinking Water factory or Household water purifier） | 40~60% | General is in-situ modified |
| 2 | Membrane module applied to desalinization | 30~40% | Strict is in-situ modified or relative The dystopy modification mode of mitigation |
| 3 | Applied to industrial special waste water isolation of purified（Such as The processing of power plant effluent, the processing of dyeing waste water） | 20%~30% | Strict dystopy modification mode |
A kind of twice-modified method of discarded reverse osmosis membrane available for treatment of dyeing wastewater proposed by the present invention, takes water process
The discarded reverse osmosis membrane obtained in technique, and discarded reverse osmosis membrane is modified according to levels of contamination using in-situ modified or dystopy
Mode carry out secondary operation, with promote waste and old reverse osmosis membrane flux, cutoff performance recover and cycling and reutilization；The pollution level
Do not divided according to the ratio of the initial use of discarded reverse osmosis membrane, existing flux and original flux；For applied to drinking water
The discarded reverse osmosis membrane of deep purifying, when flux occupies the 40 ~ 60% of original flux, is handled using general Method in situ modification,
For the discarded reverse osmosis membrane applied to desalinization, when flux occupies the 30 ~ 40% of original flux, using strict original position
The modified or relative dystopy method of modifying processing relaxed；Applied to the discarded reverse osmosis membrane of industrial special waste water isolation of purified,
When flux occupies the 20% ~ 30% of original flux, handled using strict dystopy method of modifying.
In the present invention, the general Method in situ modification is comprised the following steps that：
（1）Prerinse：Using cleaning agent to discarding reverse osmosis membrane continuous wash 12 hours；
（2）Ultrasonic wave added is cleaned：By step（1）Products therefrom carries out ultrasonic wave added cleaning, and supersonic frequency is 100 Hz, when ultrasonic
Between be 2 h；
（3）Configure the depth cleaning of film regenerative agent：By step（2）Products therefrom carries out depth with film regenerative agent and cleaned, the film
Regenerative agent composition is 30wt% potassium hydroxide, 8wt% ATMPs (ATP), 12wt% polyacrylic acid (PAA), 2wt%
Tween（T-80）With 48wt% water；
The strict Method in situ modification, is comprised the following steps that：
（1）Prerinse：Using strong detergent to discarding reverse osmosis membrane continuous wash 18 hours；
（2）Ultrasonic wave added is cleaned：By step（1）Products therefrom carries out ultrasonic wave added cleaning, and supersonic frequency is 100 Hz, when ultrasonic
Between be 4 h；
（3）Configure the depth cleaning of film regenerative agent：By step（2）Products therefrom carries out depth with film regenerative agent and cleaned, the film
Regenerative agent composition is 40wt% potassium hydroxide, 10wt% 1-hydroxy ethylidene-1,1-diphosphonic acids, 8% K-IAO, 4wt% tweens（T-80）With
38wt% water.
In the present invention, the cleaning agent that the general Method in situ modification is used is hydrochloric acid, NaOH, absolute ethyl alcohol, double
Oxygen water, sodium hypochlorite, ethylenediamine tetra-acetic acid（EDTA）, diethylene-triamine pentaacetic acid (DTPA), N-hydroxyethyl-ethylenediamine triacetic acid
Or it is any in the double 2- amino ethyl ether tetraacethyls of ethylene glycol；The strong detergent that the strict Method in situ modification is used be by
15wt% sodium alkyl sulfonates, 8wt% fatty alcohol-ether sodium sulfates, 25wt% solubilizer and 52wt% water are mixed.
In the present invention, the dystopy processing method of the relative mitigation of the discarded reverse osmosis membrane is comprised the following steps that：
（1）Remove putamina：The shell of the discarded reverse osmosis membrane of whole parcel is directly opened by the way of approximation breaks down；
（2）Prerinse diaphragm：Turned to brush away the colloid dress polluter that membrane removal surface is deposited with machinery；Machinery turns brush using relatively soft
Soft hairbrush makes brush by bafta, and brush is contacted just with film surface, and the speed of rotation is no more than 20 rpm/min,
The surface to film is eluted from cleaning agent during brush cleaning is turned, to promote the more preferable removal of pollutant；Scavenging period
For 2-3 h;
（3）Ultrasonic wave added is cleaned：By step（2）Gained diaphragm carries out ultrasonic wave added cleaning, and supersonic frequency is 100 Hz, when ultrasonic
Between be 2 h；
（4）Membrane surface modification：To step（3）Diaphragm after cleaning, membrane material surface is improved by surface graft modification mode
Hydrophilicity promotes recovering again for active layer；
（5）The redesign process of putamina：Detachable end-blocking mode is considered as, it is convenient to take out rolling diaphragm.
In the present invention, the strict dystopy method of modifying of the use of the discarded reverse osmosis membrane is comprised the following steps that：
（1）Remove putamina：The shell of the discarded reverse osmosis membrane of whole parcel is directly opened by the way of approximation breaks down；
（2）Prerinse diaphragm：Turned to brush away the colloid dress polluter that membrane removal surface is deposited with machinery；Machinery turns brush using relatively soft
Soft hairbrush makes brush by bafta, and brush is contacted just with film surface, and the speed of rotation is no more than 20 rpm/min,
The surface to film is eluted from cleaning agent during brush cleaning is turned, to promote the more preferable removal of pollutant；Scavenging period
For 2-3 h;
（3）Depth is cleaned：By step（2）Gained diaphragm be put into clear water soak, and be passed through be passed through with 0.5 L/min speed it is smelly
Oxygen, the time being passed through is 5-10 min；
（4）Membrane surface modification：To step（3）Diaphragm after middle depth cleaning, membrane material is improved by surface graft modification mode
The hydrophilicity on surface promotes recovering again for active layer；
（5）The redesign process of putamina：Detachable end-blocking mode is considered as, it is convenient to take out rolling diaphragm.
In the present invention, the step in the relative dystopy processing method relaxed and strict dystopy method of modifying（4）In
The surface graft modification mode uses any in following methods：
Method one：Reverse osmosis membrane after ultrasonic cleaning is positioned over ethanol solution and soaks 10 min, film surface is filled
Whole membrane module, is then placed into strong acid and soaks 5 min, make the abundant hydroxylating in reverse osmosis membrane assembly surface by the wetting divided.
Reverse osmosis membrane after hydroxylating is put into the oil solution that pyromellitic trimethylsilyl chloride/n-hexane is mixed to form and fully soaked, Ran Hou
Fully soaked in titanium dioxide or silica dioxide gel, so as to form the nanogel antipollution of one layer of hydrophiling on film surface
Layer, by deionized water rinsing film surface, hydrophiling graft modification film surface is ultimately formed；
Method two：Reverse osmosis membrane after ultrasonic cleaning is first molten in the mixing of 3 mol/L potassium hydroxide and 4% potassium permanganate
10 min are boiled in liquid in 80 DEG C of water-bath, the NaHSO of excess is then moved it into again3/H2SO4Sufficiently soaked,
The time of immersion is 1-2 h, to remove unnecessary alkali lye and oxidant, is then sufficiently washed with deionized water, so as to complete
The hydroxylation procedures on reverse osmosis membrane surface, are immersed in pyromellitic trimethylsilyl chloride/n-hexane by hydroxylated reverse osmosis membrane and are mixed to form
Oil solution in sufficiently immersion 30 min, then in 5 g/L poly-vinyl alcohol solution sufficiently immersion 2 h, finally by
Deionized water rinsing film surface, hydrophiling graft modification film surface is ultimately formed.
In the present invention, cleaning agent is equal described in the relative dystopy processing method relaxed and strict dystopy method of modifying
For hydrochloric acid, NaOH, absolute ethyl alcohol, hydrogen peroxide, sodium hypochlorite, ethylenediamine tetra-acetic acid（EDTA）, diethylene-triamine pentaacetic acid
(DTPA) it is, any in the double 2- amino ethyl ether tetraacethyls of N-hydroxyethyl-ethylenediamine triacetic acid or ethylene glycol.
In the present invention, the mass volume ratio of pyromellitic trimethylsilyl chloride/n-hexane is：0.6%, W/V.
The beneficial effects of the present invention are：
A) use cost of the reverse osmosis membrane in dyeing waste water is greatly reduced, is mainly shown as that the Costco Wholesale of film is reduced
30~60%。
B) film of discarded counter-infiltration is subjected to secondary operation recycling, can greatly reduces discarded membrane module to environment
Destruction.Discarded reverse osmosis membrane can not possibly return to original flux, but it still has preferable supporting layer, pervious bed
Deng still with larger value, the invention promotes the cycling and reutilization of resource.
C) according to the source of discarded reverse osmosis membrane assembly, the pollution level to film is classified, and different levels of contamination are adopted
With different ways and means so that modified more targeted, and save certain cost.
D) dystopy is modified the method chosen and can realize large-scale modified and apply, it is possible to form certain industry
Change.
E) modified reverse osmosis membrane can preferably be applied to the reuse of dyeing waste water, although rejection is than new film
Decline, be not very high to the salinity requirements of recycle-water but during the reuse of dyeing waste water, and residual fraction salinity can reduce
The addition again of part salinity.
F) modified reverse osmosis membrane performance is more stable, and surface has certain hydrophilicity, resists with certain
Pollutant performance, and the holding that effluent quality can be long-term.
Brief description of the drawings
Surface scan electromicroscopic photograph contrast situation in Fig. 1 embodiments 1 before and after reverse osmosis membrane cleaning：（a）Before cleaning,（b）
After cleaning；
Reverse osmosis membrane cleaning and modified surface scan electromicroscopic photograph contrast situation in Fig. 2 embodiments 2：（a）Before cleaning,（b）
Turn after brush and regenerative agent combined cleaning,（c）After strong acid treatment,（d）After hydrophiling grafting is titania modified；
Reverse osmosis membrane cleaning and modified surface scan electromicroscopic photograph contrast situation in Fig. 3 embodiments 3：（a）Before cleaning,（b）
Hydrophiling grafting polyvinyl alcohol is modified；
Lower flux recovery situation is not recycled for multiple times in reverse osmosis membrane to Fig. 4 in the case of be the same as Example.
Embodiment
The present invention is described in further detail with reference to embodiment.
Embodiment 1：
The flux for the discarded reverse osmosis membrane membrane module bought from municipal tap water factory is tested, and compares its initial flux, it is determined that
Its initial flux only has the 40% of original flux, it is contemplated that the initial use of reverse osmosis membrane is relatively preferable, therefore using in-situ modified
Mode the flux of film is recovered, specific process is：
（1）Pickling and alkali lye are cleaned repeatedly
Membrane module is alternately cleaned each 12 hours respectively using 5% hydrochloric acid and 5% NaOH.
（2）Ultrasonic wave added is cleaned
Ultrasonic wave added cleaning refers to that the membrane module after alternately cleaning pickling and alkali cleaning is placed into progress auxiliary cleaning in ultrasound,
The pollutant for going to membrane removal surface as more as possible.The frequency of ultrasound is 100 Hz, and ultrasonic time is 2 h.
（3）Configuration film regenerative agent is simultaneously recovered again with regenerative agent to membrane flux
The main component of regenerative agent is 30% potassium hydroxide, 8% ATMP (ATP) and 12% in the case study on implementation
Polyacrylic acid (PAA), 2% tween（T-80）, 48% water composition, regenerative agent be passed through membrane module process use circulating filtration side
Formula, the time of circulation backwash is 24 h, and rinses with clear water the regenerative agent of reverse osmosis membrane remained on surface again, and the film after cleaning leads to
Amount can return to original 85%, and then membrane module is applied in a certain specific dyeing waste water.The processing of the dyeing waste water
Process selection MBR and the technique of reverse osmosis membrane combination, mainly illustrate water quality situation of the dyeing waste water before and after reverse osmosis membrane here,
Concrete outcome is as shown in table 2：
The water quality situation before and after reverse osmosis membrane processing dyeing waste water in the embodiment 1 of table 2
| Sample sequence number | Turbidity NTU | Electrical conductivity μ s/cm | TOC mg/L | TN mg/L |
| MBR produces water | 4.830 | 18658 | 219.725 | 33.675 |
| RO concentrated waters | 6.360 | 25687 | 459.875 | 42.700 |
| RO produces water | 0.510 | 890 | 61.050 | 24.750 |
Embodiment 2：
Discarded reverse osmosis membrane in the embodiment is bought from the reverse osmosis membrane assembly in waste water from power plant technique, and it is initial to compare its
Flux, determines that its initial flux only has the 30% of original flux, illustrates that the stifled phenomenon of dirt of reverse osmosis membrane is very serious, using single
In-situ modified mode is difficult to realize the recovery of membrane flux, therefore is carried out here by the way of dystopy modification, specific process
It is as follows：
（1）Putamina is opened with cutting machine
Putamina is opened in direction with cutting machine along putamina housing, and the two ends of diaphragm in sealing membrane modules should not be destroyed as far as possible
Sealing.
（2）Turn brush rinsing membrane module
The brush that turns used is special banister brush or to make brush by bafta, at the same adjustment turn between brush and diaphragm away from
From making brush be contacted just with film surface, the speed setting for turning brush is 20 rpm/min, while with brush cleaning is turned, with configuration
The aqueous solution of good film regenerative agent is eluted, and is so more beneficial for promoting the removal of reverse osmosis membrane surface contamination material.Cleaning
Pollution removal situation of the time according to film surface depending on, generally 20 ~ 30 min.In the case study on implementation regenerative agent it is main into
Be divided into 15% hydrogen peroxide, 2% ethylene diamine tetra methylene phosphonic acid (EDTMP), 0.5% T-80 solution, 0.5% OP-10 solution,
30% acetic acid solution.Wherein Tween 80, OP-10 etc. can also be other surfactants, such as lauryl sodium sulfate, ten
Dialkyl benzene sulfonic acids sodium, sodium glycocholate.
（3）Ultrasonic wave added is cleaned
Ultrasonic wave added cleaning refers to that the membrane module after brush cleaning cleaning, the dirt gone in membrane removal and fenestra as more as possible will be turned
Contaminate thing.The frequency of ultrasound is 100 Hz, and ultrasonic time is 2 h.
（4）The hydrophiling graft modification on film surface
The reverse osmosis membrane after ultrasonic cleaning is now positioned over ethanol solution and soaks 10 min, film surface is sufficiently moistened
It is wet, then whole membrane module is placed into strong acid such as（H2SO4/HNO3=1:3）5 min are soaked, making sure to keep in mind must be when mixing
Acid liquor temperature cooling after diaphragm is put into again, film surface is carried out sufficient hydroxylating.By the reverse osmosis membrane after hydroxylating
It is put into the oil solution that pyromellitic trimethylsilyl chloride/n-hexane (0.6%, W/v) of certain volume is mixed to form and is sufficiently soaked,
Then fully soaked in titanium dioxide or silica dioxide gel, so as to form the nanogel of one layer of hydrophiling on film surface
Anti-pollution layer, by deionized water flushing membrane surface repeatedly, hydrophiling graft modification film surface is ultimately formed.Then by diaphragm weight
New is packaged, and considers to select dismountable putamina during new putamina is designed, so as to promote the recycling of putamina
With the taking-up again of diaphragm.Finally freshly prepared membrane module is applied in a certain specific dyeing waste water, before reverse osmosis membrane processing
Water quality situation afterwards is as shown in table 3：
The water quality situation before and after reverse osmosis membrane processing dyeing waste water in the embodiment 2 of table 3
| Sample sequence number | Turbidity NTU | Electrical conductivity μ s/cm | TOC mg/L | TN mg/L |
| MBR produces water | 4.830 | 18658 | 219.725 | 33.675 |
| RO concentrated waters | 6.260 | 28589 | 72.34 | 45.34 |
| RO produces water | 0.31 | 837 | 16.50 | 18.96 |
Embodiment 3：
The modifying process of the film of discarded counter-infiltration in embodiment 3 is consistent with first three step in embodiment 2, unique different
It is to employ the method that different film surface graftings are modified, the film surface prepared has hydrophilic stability persistently and more preferable
Antifouling property, the mode of graft modification is as follows.
Diaphragm after first three step is treated is first in 3 mol/L potassium hydroxide and the mixed solution of 4% potassium permanganate
10 min are boiled in 80 DEG C of water-bath, then again by NaHSO3/H2SO4Sufficiently soaked, remove unnecessary oxidant and
Alkali lye, is then sufficiently washed with deionized water, so that the hydroxylation procedures of complete film formation surface, hydroxylated reverse osmosis membrane is soaked
Sufficiently immersion 30 in the oil solution that the pyromellitic trimethylsilyl chloride/n-hexane (0.6%, W/v) steeped in certain volume is mixed to form
Min, then fully 2 h of immersion in 5 g/L poly-vinyl alcohol solution, hydrophilic finally by deionized water flushing membrane surface repeatedly
Change graft modification film surface to ultimately form.
Then being packaged again by diaphragm, easily disassembled putamina is considered into during new putamina design,
Putamina is so allowd to reuse, while after diaphragm pollutes again, can also again take out and be cleaned multiple times.
The reverse osmosis membrane prepared in the embodiment is applied in the technique that MBR and reverse osmosis membrane are combined, front and rear processing
Water quality is as shown in table 4.
The water quality situation before and after reverse osmosis membrane processing dyeing waste water in the embodiment 3 of table 4
| Sample sequence number | Turbidity NTU | Electrical conductivity us/cm | TOC mg/L | TN mg/L |
| MBR produces water | 4.830 | 18658 | 219.725 | 33.675 |
| RO concentrated waters | 6.260 | 26897 | 459.875 | 48.54 |
| RO produces water | 0.18 | 658 | 53.05 | 16.75 |
Claims (7)
1. a kind of twice-modified method of discarded reverse osmosis membrane available for treatment of dyeing wastewater, it is characterised in that take water process
The discarded reverse osmosis membrane obtained in technique, and discarded reverse osmosis membrane is modified according to levels of contamination using in-situ modified or dystopy
Mode carry out secondary operation, to promote discarded reverse osmosis membrane flux, cutoff performance to recover and cycling and reutilization；The pollution level
Do not divided according to the ratio of the initial use of discarded reverse osmosis membrane, existing flux and original flux；For applied to drinking water
The discarded reverse osmosis membrane of deep purifying, when flux occupies the 40 ~ 60% of original flux, is handled using general Method in situ modification,
For the discarded reverse osmosis membrane applied to desalinization, when flux occupies the 30 ~ 40% of original flux, using strict original position
The modified or relative dystopy method of modifying processing relaxed；Applied to the discarded reverse osmosis membrane of industrial special waste water isolation of purified,
When flux occupies the 20% ~ 30% of original flux, handled using strict dystopy method of modifying.
2. twice-modified method according to claim 1, it is characterised in that the general Method in situ modification, specific steps
It is as follows：
（1）Prerinse：Using cleaning agent to discarding reverse osmosis membrane continuous wash 12 hours；
（2）Ultrasonic wave added is cleaned：By step（1）Products therefrom carries out ultrasonic wave added cleaning, and supersonic frequency is 100 Hz, when ultrasonic
Between be 2 h；
（3）Configure the depth cleaning of film regenerative agent：By step（2）Products therefrom carries out depth with film regenerative agent and cleaned, the film
Regenerative agent composition be 30wt% potassium hydroxide, 8wt% ATMPs, 12wt% polyacrylic acid, 2wt% tweens and
48wt% water；
The strict Method in situ modification, is comprised the following steps that：
（1）Prerinse：Using strong detergent to discarding reverse osmosis membrane continuous wash 18 hours；
（2）Ultrasonic wave added is cleaned：By step（1）Products therefrom carries out ultrasonic wave added cleaning, and supersonic frequency is 100 Hz, when ultrasonic
Between be 4 h；
（3）Configure the depth cleaning of film regenerative agent：By step（2）Products therefrom carries out depth with film regenerative agent and cleaned, the film
Regenerative agent composition is 40wt% potassium hydroxide, 10wt% 1-hydroxy ethylidene-1,1-diphosphonic acids, 8% K-IAO, 4wt% tweens（T-80）With
38wt% water.
3. twice-modified method according to claim 2, it is characterised in that it is clear that the general Method in situ modification is used
Lotion is hydrochloric acid, NaOH, absolute ethyl alcohol, hydrogen peroxide, sodium hypochlorite, ethylenediamine tetra-acetic acid, diethylene-triamine pentaacetic acid, N-
It is any in hydroxyethylethylene diamine tri-acetic acid or the double 2- amino ethyl ether tetraacethyls of ethylene glycol；The strict Method in situ modification is adopted
Strong detergent is to be mixed by 15wt% sodium alkyl sulfonates, 8wt% fatty alcohol-ether sodium sulfates, 25wt% solubilizer with 52wt% water
Form.
4. twice-modified method according to claim 1, it is characterised in that the relative mitigation of the discarded reverse osmosis membrane
Dystopy processing method, is comprised the following steps that：
（1）Remove putamina：The shell of the discarded reverse osmosis membrane of whole parcel is directly opened by the way of approximation breaks down；
（2）Prerinse diaphragm：Turned to brush away the colloid dress polluter that membrane removal surface is deposited with machinery；Machinery turns brush using relatively soft
Soft hairbrush makes brush by bafta, and brush is contacted just with film surface, and the speed of rotation is no more than 20 rpm/min,
The surface to film is eluted from cleaning agent during brush cleaning is turned, to promote the more preferable removal of pollutant；Scavenging period
For 2-3 h;
（3）Ultrasonic wave added is cleaned：By step（2）Gained diaphragm carries out ultrasonic wave added cleaning, and supersonic frequency is 100 Hz, when ultrasonic
Between be 2 h；
（4）Membrane surface modification：To step（3）Diaphragm after cleaning, membrane material surface is improved by surface graft modification mode
Hydrophilicity promotes recovering again for active layer；
（5）The redesign process of putamina：Detachable end-blocking mode is considered as, it is convenient to take out rolling diaphragm；
The strict dystopy method of modifying of the use of the discarded reverse osmosis membrane, is comprised the following steps that：
（1）Remove putamina：The shell of the discarded reverse osmosis membrane of whole parcel is directly opened by the way of approximation breaks down；
（2）Prerinse diaphragm：Turned to brush away the colloid dress polluter that membrane removal surface is deposited with machinery；Machinery turns brush using relatively soft
Soft hairbrush makes brush by bafta, and brush is contacted just with film surface, and the speed of rotation is no more than 20 rpm/min,
The surface to film is eluted from cleaning agent during brush cleaning is turned, to promote the more preferable removal of pollutant；Scavenging period
For 2-3 h；
（3）Depth is cleaned：By step（2）Gained diaphragm be put into clear water soak, and be passed through be passed through with 0.5 L/min speed it is smelly
Oxygen, the time being passed through is 5-10 min；
（4）Membrane surface modification：To step（3）Diaphragm after middle depth cleaning, membrane material is improved by surface graft modification mode
The hydrophilicity on surface promotes recovering again for active layer；
（5）The redesign process of putamina：Detachable end-blocking mode is considered as, it is convenient to take out rolling diaphragm.
5. twice-modified method according to claim 4, it is characterised in that the relative dystopy processing method relaxed and
Step in strict dystopy method of modifying（4）Described in surface graft modification mode use following methods in it is any：
Method one：Reverse osmosis membrane after ultrasonic cleaning is positioned over ethanol solution and soaks 10 min, film surface is filled
Whole membrane module, is then placed into strong acid and soaks 5 min, make the abundant hydroxylating in reverse osmosis membrane assembly surface by the wetting divided,
Reverse osmosis membrane after hydroxylating is put into the oil solution that pyromellitic trimethylsilyl chloride/n-hexane is mixed to form and fully soaked, Ran Hou
Fully soaked in titanium dioxide or silica dioxide gel, so as to form the nanogel antipollution of one layer of hydrophiling on film surface
Layer, by deionized water rinsing film surface, hydrophiling graft modification film surface is ultimately formed；
Method two：Reverse osmosis membrane after ultrasonic cleaning is first molten in the mixing of 3 mol/L potassium hydroxide and 4% potassium permanganate
10 min are boiled in liquid in 80 DEG C of water-bath, the NaHSO of excess is then moved it into again3/H2SO4Sufficiently soaked,
The time of immersion is 1-2 h, to remove unnecessary alkali lye and oxidant, is then sufficiently washed with deionized water, so as to complete
The hydroxylation procedures on reverse osmosis membrane surface, are immersed in pyromellitic trimethylsilyl chloride/n-hexane by hydroxylated reverse osmosis membrane and are mixed to form
Oil solution in sufficient 30 min of immersion, then fully 2 h of immersion in 5 g/L poly-vinyl alcohol solution, finally by going
Ionized water flushing membrane surface, hydrophiling graft modification film surface is ultimately formed.
6. twice-modified method according to claim 4, it is characterised in that the relative dystopy processing method relaxed and
Cleaning agent is hydrochloric acid, NaOH, absolute ethyl alcohol, hydrogen peroxide, sodium hypochlorite, second two described in strict dystopy method of modifying
Appoint in the double 2- amino ethyl ether tetraacethyls of amine tetraacethyl, diethylene-triamine pentaacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid or ethylene glycol
It is a kind of.
7. twice-modified method according to claim 5, it is characterised in that the quality volume of pyromellitic trimethylsilyl chloride/n-hexane
Than for：0.6%, W/V.
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| CN108380057A (en) * | 2018-03-01 | 2018-08-10 | 同济大学 | A kind of cleaning and regeneration method of the discarded reverse osmosis membrane irreversible membrane fouling object based on treatment of dyeing wastewater |
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| CN112999881B (en) * | 2021-03-17 | 2021-11-12 | 同济大学 | Method for treating scrapped PVDF (polyvinylidene fluoride) membrane by recycling water |
| CN113058437A (en) * | 2021-03-23 | 2021-07-02 | 西北农林科技大学 | Film pollution prevention and control method based on removable and renewable surface coating |
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