CN110482649A - Method of the group technology regeneration for the nano composite membrane of micropollutants removal in water - Google Patents
Method of the group technology regeneration for the nano composite membrane of micropollutants removal in water Download PDFInfo
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- CN110482649A CN110482649A CN201910671595.6A CN201910671595A CN110482649A CN 110482649 A CN110482649 A CN 110482649A CN 201910671595 A CN201910671595 A CN 201910671595A CN 110482649 A CN110482649 A CN 110482649A
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- 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
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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
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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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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Abstract
Method the present invention relates to group technology regeneration for the carbon nano composite membrane of micropollutants removal in water.And the regeneration method of effective carbon nano composite membrane, the recycling of carbon nano composite membrane may be implemented, extend the service life of carbon nano composite membrane.The present invention is that individually regeneration method is difficult to realize the effective regeneration of carbon nano composite membrane in solving the problems, such as to study at present, and exploitation regeneration technology includes preparation load liquid, the preparation of composite membrane, the filtering of compound film at low pressure, the regeneration of composite membrane physical-chemical group technology.This technique effectively realizes desorption of micro- pollution on carbon nano composite membrane using the method for the physics and chemical method combining and regenerating of cleanliness without any pollution.The physicochemical properties of the carbon nano composite membrane of the front and back of group technology regeneration simultaneously are stablized, this be carbon nanomaterial in engineering of water treatment using providing theoretical foundation and technological guidance.
Description
Technical field
The invention belongs to water-treatment technology fields, are related to a kind of membrane filtration system, and in particular to one kind is based on nano combined
The regeneration method of membrane filtration system.
Background technique
Novel nano-material carbon nanotube and the market price of graphene are $ 100-45,000K respectively-1With $ 1,200-
228,000Kg-1, and the market price of the more active carbon of practical application is $ 0.67-75Kg-1Due to carbon nanomaterial valuableness
Price, effective regeneration method help to promote application of the carbon nanomaterial in practical water process.Currently, carbon nanomaterial
Regeneration method has very much, mainly includes chemical regeneration method, regeneration method, hot recycling method and microwave heating regeneration method.
Wherein chemical regeneration method is widely used by the active force between reduction pollutant and carbon nanomaterial
In the regeneration of carbon nanomaterial.Desorption quantity of the ultrasound enhancing micropollutants on carbon nanomaterial is due to ultrasonic cavitation
The vibration, collapse and cracking of high-energy can be generated, to weaken the active force between micropollutants and carbon nanomaterial, is promoted
Into desorption of the micropollutants on carbon nanomaterial.It can be regenerated in combination with chemical regeneration method and physics using group technology
The advantages of method, optimizes the method for regeneration treatment, extends the service life of carbon nano composite membrane, to be pushed further into carbon nanometer material
Expect the application in practical water process.
Summary of the invention
The purpose of the present invention is to provide a kind of group technologies of highly efficient regeneration MWCNT composite membrane, make carbon nano composite membrane
It is able to carry out long-term filtering, is prolonged the service life.
The purpose of the present invention is what is be achieved through the following technical solutions:
Carbon nano composite membrane of the group technology regeneration for micropollutants removal in water, it is characterised in that present invention incorporates
The physical method and chemical method of cleanliness without any pollution, effectively realize the regeneration of carbon nano composite membrane.
Physical method: sonification power: 10-20kHZ, ultrasonic time 15-60min
Chemical method: 0.01-1.0M NaCl regeneration washing liquid
Carbon nano composite membrane of the group technology regeneration for micropollutants removal in water, the regeneration condition after optimization are as follows:
Physical method: sonification power: 20kHZ, ultrasonic time 30min
Chemical method: 0.1M NaCl regeneration washing liquid
Carbon nano composite membrane of the group technology regeneration of the present invention for micropollutants removal in water, it is characterised in that:
The present invention has been effectively combined the chemical cleaning method and physics ultrasonic method of cleanliness without any pollution, and it is multiple in carbon nanometer to realize micropollutants
Close the desorption on film.
The present invention has the advantage that
Firstly, the preparation process for the carbon nano composite membrane that the present invention uses is simple: commercialization purchase MWCNT, outer diameter are
5-60nm, 1-30 μm of length, oxygen content (mass percentage) 1.2-4.1%, and and deionized water according to 1mg/1mL=1
Ratio mixing, and carry out with Ultrasonic Cell Disruptor the ultrasonic treatment of 10-15min respectively；It is using suction method that the above MWCNT is suspended
Liquid is prepared into MWCNT composite membrane；
Then, present invention employs the sodium chloride solution chemical cleaning methods of cleanliness without any pollution to the micro- pollution of filtering
MWCNT film is regenerated, and the regeneration method for regenerating common Mathanol regenerating method and ethyl alcohol with film compares, and finds NaCl
The regeneration effect of solution is best.
Then, the physics regeneration method of present invention combination non-environmental-pollution, further improves the revival of NaCl solution
Fruit, while passing through the regeneration effect of group technology under comparative analysis different ultrasonic power and ultrasonic time, optimum organization technique
Treatment conditions.
Finally, being compared point by surface topography to group technology treated carbon nanomaterial and chemical property
Analysis illustrates the mechanism of regenerative process, evaluates influence of the combination regeneration treatment process to carbon nanomaterial.
Detailed description of the invention
Fig. 1 paracetamol (AAP), brufen (IBU) and triclosan (TCS) are in original carbon nano composite membrane and variety classes
Chemical cleaning solution regeneration after adsorption capacity on carbon nano composite membrane.Micropollutants concentration=1mg L-1, pH=7.0, add up
Per membrane area water flux density=62.3L m-2, carbon nanotube mass=30mg, temperature=25 ± 2 DEG C
MWCNT composite membrane is to paracetamol (AAP), brufen after the original MWCNT composite membrane of Fig. 2 and chemistry/ultrasound regeneration
(IBU) and the adsorption capacity of triclosan (TCS), micropollutants concentration=1mg L-1, pH=7.0, accumulative units area filtrate body
Product=174L m-2, CNT mass=30mg, temperature=25 ± 2 DEG C
MWCNT composite membrane is to paracetamol (AAP), brufen after the original MWCNT composite membrane of Fig. 3 and chemistry/ultrasound regeneration
(IBU) and the adsorption capacity of triclosan (TCS), micropollutants concentration=1mg L-1, pH=7.0, accumulative units area filtrate body
Product=174L m-2, CNT mass=30mg, temperature=25 ± 2 DEG C
Fig. 4 paracetamol (AAP) under optimal ultrasonic time, brufen (IBU) and triclosan (TCS) are on the carbon nanotubes
Continuous five periods (a) adsorption capacity (b) desorbs rate than desorption quantity and (c).Micropollutants concentration=1mg L-1, pH=
7.0, accumulative units membrane area filtration flux=174L m-2, CNT mass=30mg, temperature=25 ± 2 DEG C
Fig. 5 chemical regeneration method and ultrasonic method of reproduction mechanism schematic diagram
The original MWCNT of Fig. 6 (a), (b) transmission electron microscope picture of the regeneration treatment of physical-chemical group technology and MWCNT and its right
The XPS analysis figure of (c-d) C1s answered
Specific embodiment
The present invention will be described with example with reference to the accompanying drawing.
As shown in Figure 1, using commercialized MWCNT, outer diameter 10-20nm, 10-30 μm of length, oxygen content 2.1%,
And it mixes, and is carried out respectively with Ultrasonic Cell Disruptor at the ultrasound of 10-15min according to the ratio of 1mg/1mL=1 with deionized water
Reason；Chemical method regenerative carbon nano composite membrane receives the carbon after cleaning mainly using methanol, ethyl alcohol and sodium chloride as cleaning agent
The adsorption capacity again of rice composite membrane is compared.The result shows that the adsorption capacity of carbon nano composite membrane is higher than after sodium chloride cleaning
The adsorption capacity of carbon nano composite membrane after methanol and ethyl alcohol cleaning, and sodium chloride is pollution-free to clean environment and is easy to back
It receives, therefore the chemical cleaning of this research is using sodium chloride as cleaning solution.Sodium chloride to the preferable desorption effect of micropollutants be due to
Sodium ion has replaced the sodium ion being adsorbed on carbon nanomaterial, to promote desorption of the micropollutants on CNT.
Specific regeneration method is as follows:
1) commercialization purchase MWCNT, outer diameter 5-60nm, 1-30 μm of length, oxygen content 1.2-4.1%, and with go
Ionized water is mixed according to the ratio of 1mg/1mL=1, and carries out the ultrasonic treatment of 10-15min respectively with Ultrasonic Cell Disruptor；
2) with pore size for 0.1-0.22 microns, surface area is 4.52 × 10-4m2PVDF membrane (PVDF)
Or polyvinyl chloride (PVC) is substrate, and the MWCNT suspension in 1) is prepared into MWCNT composite membrane using suction method；
3) using the micropollutants in the method filtering water body of dynamic filtration, until MWCNT made above filters saturation,
Then the MWCNT film of filtering saturation is put into the NaCl solution that concentration is 0.01-1.0M, is in power with ultrasonic cleaning instrument
The ultrasonic treatment of 15-60min is carried out under conditions of 10-20kHZ；
4) then the MWCNT composite membrane after the regeneration of the above chemical method is carried out to the filtering of second of micropollutants, discovery
It is power by regeneration condition is 20kHZ, ultrasonic time is that the filtering of the MWCNT film and original membrane after 30min ultrasonic treatment is imitated
Rate is closest；
5) the chemical property comparative analysis of the surface topography of the MWCNT of regeneration front and back and surface, discovery MWCNT regeneration front and back
Physics and chemical property stablize.
In order to further probe into regeneration effect of the concentration to MWCNT composite membrane of sodium chloride cleaning solution, the chlorine of various concentration
Change the regeneration for being used to MWCNT composite membrane that sodium solution includes 0.01M, 0.1M and 1.0M.As shown in Fig. 2, the sodium chloride of 0.1M
The adsorption capacity of carbon nano composite membrane after solution cleaning is maximum, and followed by the sodium chloride solution of 1.0M, the sodium chloride of 0.01M are molten
The suction desorption ability of carbon nano composite membrane after liquid cleaning is the smallest.Therefore, the chemical regeneration method of this research is with 0.1M
Sodium chloride is what cleaning solution carried out.
Although chemical method regenerative carbon nano composite membrane achieves certain effect, but chemical method and ultrasonic method combine it is clear
Washing method further improves the regeneration effect of carbon nano composite membrane.Due in ultrasonic desorption process, fixing a ultrasonic power,
Probe into the influence of regeneration effect using ultrasonic time as variable, the ultrasonic time of 15min, 30min and 60min are respectively used to carbon and receive
In the regeneration of rice composite membrane.As shown in Figure 3a, after ultrasonic treatment, the adsorption capacity of AAP and TCS with ultrasonic time increasing
Add and increase, but certain decline occurs instead under the ultrasound condition of 60min in the adsorption capacity of IBU.The solution of AAP simultaneously
Energy-absorbing power is continuously improved with the increase of the ultrasonic time in 15-60min, but IBU and TCS is more than 30min in ultrasonic time
After, ultrasound is smaller to the raising of the regeneration effect of carbon nano composite membrane.Therefore, for IBU, the ultrasonic time of 30min is recognized
To be most economical effective regeneration ultrasonic time, and 60min is then the best regeneration ultrasonic time of AAP and TCS.
Under optimal ultrasonic desorption condition, the adsorption capacity of the carbon nanotube after regeneration is 1.99mg g-1, i.e., by super
Adsorption capacity 2.13mg g after sonication, with original carbon nanotube-1It compares, the adsorption capacity of 96% carbon nanotube obtains
Restore, in similar optimal ultrasonic regeneration condition, the adsorption capacity of IBU and TCS can be restored to original carbon nanomaterial
95%.To sum up, by the ultrasonic regeneration treatment of optimal conditions, most of absorption regeneration ability of carbon nanotube has obtained extensive
It is multiple.
To sum up, chemical method combination ultrasonic method significantly enhances the desorption ability of micropollutants.It is super in order to further verify
The effect of acoustic regeneration, this research have carried out the regeneration period of five continuous adsorption-desorptions.As shown in figure 4, the adsorption capacity of AAP
From 1.99mg g in continuous five periods-1It is reduced to 1.60mg g-1, but the desorption ability of AAP is maintained at 0.25mg g-1-0.30mg g-1.In comparison, adsorption capacity of the adsorption capacity of IBU less than AAP, but its desorption ability ratio AAP
Desorption ability it is slightly higher, reached 0.51mg g-1-0.77mg g-1.And for triclosan, adsorption capacity and energy of desorption
Power is relatively high, and its highest adsorption capacity and desorption ability are respectively 3.28mg g-1With 1.31mg g-1。
Fig. 5 illustrates the mechanism of combination regeneration method, and the process of chemical regeneration is primarily directed to carbon nanomaterial and micro- dirt
The interaction force between object is contaminated, the carbon nano composite membrane of adsorption saturation is carried out using the chemical reagent for weakening the above active force
Regeneration washing.It is found in probing into the regenerative process of methanol, ethyl alcohol and NaCl solution to carbon nano composite membrane, the NaCl of 0.1M is molten
Liquid be to the regeneration effect of carbon nano composite membrane it is optimal, this is mainly due to the Na in NaCl solution+It has replaced and has been adsorbed on
The micropollutants on the surface MWCNT, to realize the regeneration (Fig. 5) of carbon nano composite membrane.
The regenerated process of ultrasound is mainly generation and the cracking process of cavitation bubble.These cavitation bubbles pass through in water body
After of short duration several microseconds rise, bubbles burst, while powerful shearing force (Fig. 5) is produced around, it enhances and is adsorbed on
Vibration, the desorption of the micropollutants on the surface MWCNT.The high temperature action generated during bubble cracking simultaneously can also weaken micro-
Interaction force between pollutant and MWCNT.Therefore, when chemical cleaning is in conjunction with the removal of AAP, IBU and TCS when being cleaned by ultrasonic
Efficiency is improved to some extent.
The size of the adsorption capacity of MWCNT and the chemical property on the surface MWCNT have close relationship, and MWCNT is by ultrasound
Its chemical property is possible to be changed after processing, therefore this research characterizes the property of the MWCNT of regeneration front and back.Such as figure
Shown in 6, MWCNT before and after the processing is the structure of the tubulose of similar flexion, it is meant that structure of the regeneration treatment to the surface MWCNT
It influences smaller.The result of XPS also indicates that original MWCNT, and the oxygen content of MWCNT is respectively 2.1% and 2.2% after ultrasound regeneration.
To sum up phenetic analysis, chemical-physical group technology physicochemical properties in regenerative process are stablized, and are the efficient of carbon nanomaterial
And the regeneration method of cleanliness without any pollution provides theoretical foundation and technological guidance.
Claims (3)
1. method of the group technology regeneration for the carbon nano composite membrane of micropollutants removal in water, which is characterized in that combine
The physical method and chemical method of cleanliness without any pollution, realize the regeneration of carbon nano composite membrane:
Physical method: Ultrasonic Cell Disruptor processing power: 10-20kHZ, ultrasonic time 15-60min
Chemical method: 0.01-1.0M NaCl regeneration washing liquid.
2. the method according to claim 1, wherein regeneration condition is as follows:
Physical method: ultrasonic with Ultrasonic Cell Disruptor: 20kHZ, ultrasonic time 30min
Chemical method: 0.1M NaCl regeneration washing liquid.
3. according to claim 1 or method described in 2, it is characterised in that method is as follows:
1) MWCNT, outer diameter 5-60nm are bought, 1-30 μm of length, oxygen-containing mass percentage is 1.2-4.1%, and
MWCNT and deionized water are mixed according to the ratio of 1mg/mL=1, and the ultrasonic treatment of 10-15min is carried out with Ultrasonic Cell Disruptor；
2) using PVDF membrane or polyvinyl chloride as substrate, the MWCNT suspension in 1) is prepared into using suction method
MWCNT composite membrane；
3) using the micropollutants in the method filtering water body of dynamic filtration, until MWCNT made above filters saturation, then
The MWCNT film of filtering saturation is put into the NaCl solution that concentration is 0.01-1.0M, is 10- with instrument is cleaned by ultrasonic in power
The ultrasonic treatment of 15-60min is carried out under conditions of 20kHZ.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253056A (en) * | 2005-03-14 | 2006-09-21 | Univ Nagoya | Plasma generator |
| CN104548973A (en) * | 2014-12-18 | 2015-04-29 | 东华大学 | Preparation and catalytic regeneration of functionalized graphene oxide/polyether sulfone blended ultrafiltration membrane |
| CN105561810A (en) * | 2015-12-22 | 2016-05-11 | 北京理工大学 | Method of using carbon nanofiber layer to modify ultrafiltration membrane |
| CN108479712A (en) * | 2018-03-28 | 2018-09-04 | 中山大学 | A kind of the modified carbon nano-tube thin-film material and its application process of adsorbable degrading tetrabromobisphenol A |
-
2019
- 2019-07-24 CN CN201910671595.6A patent/CN110482649A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253056A (en) * | 2005-03-14 | 2006-09-21 | Univ Nagoya | Plasma generator |
| CN104548973A (en) * | 2014-12-18 | 2015-04-29 | 东华大学 | Preparation and catalytic regeneration of functionalized graphene oxide/polyether sulfone blended ultrafiltration membrane |
| CN105561810A (en) * | 2015-12-22 | 2016-05-11 | 北京理工大学 | Method of using carbon nanofiber layer to modify ultrafiltration membrane |
| CN108479712A (en) * | 2018-03-28 | 2018-09-04 | 中山大学 | A kind of the modified carbon nano-tube thin-film material and its application process of adsorbable degrading tetrabromobisphenol A |
Non-Patent Citations (1)
| Title |
|---|
| YIFEI WANG ET AL.: "Comparison of chemical, ultrasonic and thermal regeneration of carbon nanotubes for acetaminophen", 《RSC ADVENCES》 * |
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