CN107096388A - A kind of forward osmosis membrane cleaning method - Google Patents
A kind of forward osmosis membrane cleaning method Download PDFInfo
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- CN107096388A CN107096388A CN201710299202.4A CN201710299202A CN107096388A CN 107096388 A CN107096388 A CN 107096388A CN 201710299202 A CN201710299202 A CN 201710299202A CN 107096388 A CN107096388 A CN 107096388A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/02—Forward flushing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/04—Backflushing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of forward osmosis membrane cleaning method, belong to sewage treatment area.The forward osmosis membrane cleaning method of the present invention combines physical cleaning and Chemical cleaning；Surface washing is carried out with deionized water to the forward osmosis membrane of pollution, reversible pollutant is removed；Biological pollutant and organic pollution that FO pollutes film surface are removed by the oxidation of hydrogen peroxide；Inorganic pollution is removed using hydrochloric acid；The pollutant remained after Chemical cleaning is removed using backwash.The inventive method is scientific and reasonable, to the problem for overcoming forward osmosis membrane to pollute, and expands application of the forward osmosis membrane in sewage disposal significant.
Description
Technical field
The present invention relates to a kind of forward osmosis membrane cleaning method, belong to sewage treatment area.
Background technology
With world water resources and the worsening shortages of the energy, water resource has been subjected to the concern of more and more people.Due to
The resources such as abundant water resource and a large amount of C, N, P are contained, municipal sewage has been counted as a kind of resource.In this context,
Urban sewage treatment process for the purpose of reusing sewage and energy recovery will more and more be paid attention to.Combine anaerobism
The anaerobism forward osmosis membrane bioreactor (AnOMBR) of biotechnology and forward osmosis membrane isolation technics is used as a kind of new film point
Paid close attention to from technology by increasing scholar.It mainly replaces anaerobic membrane bioreactor using positive infiltration (FO) film
(AnMBR) micro-filtration (MF) film or milipore filter (UF) in.With pass AnMBR compared with, AnOMBR by FO films efficient rejection
Can, effluent quality is improved, water outlet is directly carried out reuse；Simultaneously because the low stain characteristic of FO films, to a certain degree
On alleviate fouling membrane.
Compared with pressure-actuated MF films, the pollution tendencies of FO films are although relatively low in AnOMBR, but there is also more serious
Fouling membrane.The pollution type of FO films is mainly the compound pollution based on organic contamination and biological pollution in AnOMBR.Sternly
The fouling membrane of weight causes the blocking of FO films, causes the decline of FO membrane fluxs, have impact on AnOMBR stable operation, is badly in need of finding and closes
Suitable cleaning way recovers the runnability of FO films.
At present, commercial FO films only have two kinds of materials of acetate fiber (CTA) and polyamide (TFC).For CTA-FO films,
The cleaning method having been reported that includes physical cleaning and Chemical cleaning.Physical cleaning mainly uses the interaction of power to make film surface
Pollutant departs from from film surface.The physical cleaning for the CTA-FO films reported at present includes surface washing and backwash.Physical cleaning
Advantage is removal film surface pollution thing, thing when fouling membrane is lighter on the basis of the physicochemical characteristics of membrane material is not destroyed
Clear and wash with preferable effect, but when fouling membrane is heavier, the effect of physical cleaning is very limited.In physical cleaning effect not
When good, what is generally used is exactly Chemical cleaning.Chemical cleaning is mainly used between Chemical cleaning reagent and film surface pollution material
Generation chemical reaction makes pollutant depart from from film surface, and its advantage is fast and effectively removal film surface pollution thing, but there is destruction film
The danger of performance.The medicament that CTA-FO films Chemical cleaning is used mainly includes sodium hypochlorite, sodium hydroxide, citric acid and hydrochloric acid
Deng.Because the antifouling property of CTA-FO films is preferable, therefore, it can just be obtained using conventional physical cleaning or Chemical cleaning
Preferable effect.
For TFC-FO films, the cleaning method having been reported is also physical cleaning or Chemical cleaning.Compared with CTA-FO films,
TFC-FO films surface is relatively rough, and fouling membrane is heavier.In addition, the membrane material of all TFC materials is poor to the tolerance of chlorine, not
Can be using sodium hypochlorite cleaning.In the case of this these, the physical cleaning and chemical cleaning method commonly used using CTA-FO films all without
Method effectively cleans TFC-FO films.Therefore, it is badly in need of finding effectively TFC-FO Membrane cleanings method.
The content of the invention
It is clear with the FO polluted membranes that Chemical cleaning is combined the invention provides a kind of physical cleaning in order to solve the above problems
Washing method, it is effective to remove the pollutant that FO pollutes film surface；Surface washing in physical cleaning is mainly used in rinsing FO films surface
Loose pollutant；Chemical cleaning is mainly selection hydrogen peroxide as main cleaning agent, additional certain density hydrochloric acid auxiliary, deep
Degree remove FO film surfaces pollutant, and under the auxiliary of hydrochloric acid reduce hydrogen peroxide concentration；Backwash master in physics flushing
Remove the pollutant loosened after Chemical cleaning.The inventive method, is rinsed, removal can to the FO films of pollution with deionized water
Inverse pollutant；Biological pollutant and organic pollution that FO pollutes film surface are removed by the oxidation of hydrogen peroxide；Using
Hydrochloric acid removes inorganic pollution；The pollutant remained after Chemical cleaning is removed using backwash.
The present invention is mainly to provide the FO fouling membrane cleaning ways that a kind of physical cleaning is combined with Chemical cleaning, including step
Suddenly：
(1) surface washing is carried out with water to the FO films of pollution；
(2) the FO films after flushing are immersed in hydrogenperoxide steam generator；
(3) FO films are taken out from hydrogenperoxide steam generator, then film surface is rinsed with water, be then immersed in hydrochloric acid solution；
(4) FO films are taken out, in immersion sodium chloride solution, backwashed using water as liquid is drawn.
In one embodiment, the FO films are the film of polyamide material.
In one embodiment, the FO films are the FO films in anaerobism forward osmosis membrane bioreactor.
In one embodiment, it is 10~20min to the surface washing time of the FO films of pollution in step (1).
In one embodiment, the hydrogenperoxide steam generator concentration described in step (2) is 0.1~0.2% (v/v).
In one embodiment, hydrogenperoxide steam generator temperature used in step (2) is 22~28 DEG C.
In one embodiment, the time of immersion hydrogenperoxide steam generator is 1~3h in step (2).
In one embodiment, the concentration of hydrochloric acid solution described in step (3) is 0.8~1.2% (v/v).
In one embodiment, hydrochloric acid solution temperature used in step (3) is 22~28 DEG C.
In one embodiment, the time of immersion hydrochloric acid solution is 0.6~1.5h in step (3).
In one embodiment, the concentration of the sodium chloride solution described in step (4) is 15~25mM.
In one embodiment, the backwashing time described in step (4) is 5~10min.
In one embodiment, the water in methods described is deionized water.
The present invention proposes the method that Chemical cleaning is combined with physical cleaning.The inventive method, it is dirty according to TFC-FO films
The characteristic of dye, removes film surface pollution thing using Chemical cleaning first or loosens film surface pollution thing, then pass through physical cleaning removalization
Learn the pollutant that cleaning loosens and remained.The present invention is, using physical cleaning after first Chemical cleaning, to be adopted with current all Membrane cleanings
Chemical cleaning after independent Chemical cleaning or physical cleaning and first physical cleaning, there is the difference of essence from Cleaning principle.
In addition, the chemical that the present invention is used is hydrogen peroxide and hydrochloric acid.At present, the report that FO films are not cleaned using hydrogen peroxide,
It is that can use hydrogen peroxide only in reverse osmosis membrane cleaning, mainly removes removal organic polluter and sterilization.But, because hydrogen peroxide can be right
Membrane material produces destruction, how effectively to reduce its concentration and time of contact is just critically important.Synergy of the invention by hydrochloric acid,
By a series of research, the concentration of hydrogen peroxide is reduced to 0.1% (v/v), film is extended while cleaning performance is ensured
Life-span.
Compared with the forward osmosis membrane cleaning method having been reported, the present invention at least has advantages below：
(1) hydrogenperoxide steam generator used in the present invention is as a kind of oxidant, the effect for removing FO film surface pollution things
It is excellent.
(2) present invention, by synergy, reduces hydrogen peroxide by the way of hydrochloric acid auxiliary hydrogen peroxide cleaning
Concentration, reduces the damage to FO films, extends the service life of film.
(3) cleaning program of the invention is a kind of mode that physical cleaning is combined with Chemical cleaning, and Chemical cleaning can
The effect that physical cleaning removes film surface pollution thing is made up, physical cleaning can reduce what Chemical cleaning changed to film surface material character
Trend；The first Chemical cleaning mode that physics is backwashed again, enhances cleaning performance.
Embodiment
With reference to embodiment, the embodiment to the present invention is described in further detail.Following examples are used for
Illustrate the present invention, but be not limited to the scope of the present invention.
Embodiment 1
The object of the present embodiment method effect is in the pollution for being unable to run in the AnOMBR of salinity in control device
TFC-FO films (the FO membrane fluxs being unable in control device in the AnOMBR of salinity are smaller by the influence of salinity, and during operation
Between it is shorter), its runnability before through over cleaning is：Organic matter TOC rejection has reached 98.0%, total phosphorus TP retention
Rate has nearly reached 100%.Initial flux when TFC-FO films are run in device simultaneously is 7.99LMH, and operation is led to after 15 days
Amount decays to 2LMH, and flux fall off rate is 0.4LMH/d.Specific cleaning step is as follows：
(1) the TFC-FO films of pollution are taken out out of device, surface washing 15min is directly carried out using deionized water.
(2) in the TFC-FO films immersion hydrogenperoxide steam generator after being rinsed 1h is soaked, wherein hydrogenperoxide steam generator
Concentration is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(3) the TFC-FO films after cleaning are taken out, surface washing 5min is carried out using deionized water, hydrochloric acid is then immersed in molten
1h is soaked in liquid, the wherein concentration of hydrochloric acid solution is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(4) TFC-FO after cleaning is placed in 20mM sodium chloride solution, using deionized water as liquid is drawn, carried out
10min backwash, removes the pollutant of film surface residual and the cleaning agent of residual.
After above-mentioned cleaning, TFC-FO films are replaced in operation in AnOMBR devices and obtain following service data：
Initial flux when TFC-FO films after cleaning are run in AnOMBR devices is reduction of speed under 7.27LMH, its flux
Rate is 0.41LMH/d.Rejection to TOC is 98.5%, and the rejection to TP has nearly reached 100%.This with before cleaning
Effect is the same.This illustrates that the cleaning program can effectively remove the pollutant on FO films surface, recovers the runnability of FO films, and
And do not result in the damage of film.
Embodiment 2
The object of the present embodiment method effect is in the pollution for being unable to run in the AnOMBR of salinity in control device
TFC-FO films (the FO membrane fluxs being unable in control device in the AnOMBR of salinity are smaller by the influence of salinity, and during operation
Between it is shorter), its runnability before through over cleaning is：TOC rejection has reached that 98.0%, TP rejection is nearly reached
100%.Initial flux when TFC-FO films are run in device simultaneously is 7.99LMH, and flux decline is arrived after running 15 days
2LMH, flux fall off rate is 0.4LMH/d.Specific cleaning step is as follows：
(1) the TFC-FO films of pollution are taken out out of device, surface washing 15min is directly carried out using deionized water.
(2) in the TFC-FO films immersion hydrogenperoxide steam generator after being rinsed 3h is soaked, wherein hydrogenperoxide steam generator
Concentration is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(3) the TFC-FO films after cleaning are taken out, surface washing 5min is carried out using deionized water, hydrochloric acid is then immersed in molten
1h is soaked in liquid, the wherein concentration of hydrochloric acid solution is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(4) TFC-FO after cleaning is placed in 20mM sodium chloride solution, using deionized water as liquid is drawn, carried out
10min backwash, removes the pollutant of film surface residual and the cleaning agent of residual.
After above-mentioned cleaning, TFC-FO films are replaced in operation in AnOMBR devices and obtain following service data：
Initial flux when TFC-FO films after cleaning are run in AnOMBR devices is 8.11LMH, flux fall off rate
For 0.38LMH/d.Rejection to TOC is 98.5%, and the rejection to TP has nearly reached 100%.This illustrates the cleaning side
Case can effectively remove the pollutant on FO films surface, recover the runnability of FO films.
Embodiment 3
The object of the present embodiment method effect is in the pollution that can be run effectively in control device in the AnOMBR of salinity
(FO membrane fluxs that can be effectively in control device in the AnOMBR of salinity are influenceed smaller to TFC-FO films by salinity, and can transport
The row long period), its runnability before through over cleaning is：TOC rejection has reached 98.0%, TP rejection almost
Reach 100%.Initial flux when TFC-FO films are run in device simultaneously is 7.77LMH, flux decline after running 25 days
To 2LMH, flux fall off rate is 0.23L MH/d.Specific cleaning step is as follows：
(1) the TFC-FO films of pollution are taken out out of device, surface washing 15min is directly carried out using deionized water.
(2) in the TFC-FO films immersion hydrogenperoxide steam generator after being rinsed 1h is soaked, wherein hydrogenperoxide steam generator
Concentration is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(3) the TFC-FO films after cleaning are taken out, surface washing 5min is carried out using deionized water, hydrochloric acid is then immersed in molten
1h is soaked in liquid, the wherein concentration of hydrochloric acid solution is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(4) TFC-FO after cleaning is placed in 20mM sodium chloride solution, using deionized water as liquid is drawn, carried out
10min backwash, removes the pollutant of film surface residual and the cleaning agent of residual.
After above-mentioned cleaning, TFC-FO films are replaced in operation in AnOMBR devices and obtain following service data：
Initial flux when TFC-FO films after cleaning are run in AnOMBR devices is 7.46LMH, flux fall off rate
For 0.23LMH/d.Rejection to TOC is 98.5%, and the rejection to TP has nearly reached 100%.This and the effect before cleaning
Fruit is the same.This illustrates that the cleaning program can effectively remove the pollutant on FO films surface, recovers the runnability of FO films.
Embodiment 4
The object of the present embodiment method effect is in the pollution that can be run effectively in control device in the AnOMBR of salinity
(FO membrane fluxs that can be effectively in control device in the AnOMBR of salinity are influenceed smaller to TFC-FO films by salinity, and can transport
The row long period), its runnability before through over cleaning is：TOC rejection has reached 98.0%, TP rejection almost
Reach 100%.Initial flux when TFC-FO films are run in device simultaneously is 7.77LMH, flux decline after running 25 days
To 2LMH, flux fall off rate is 0.23LMH/d.Specific cleaning step is as follows：
(1) the TFC-FO films of pollution are taken out out of device, surface washing 15min is directly carried out using deionized water.
(2) in the TFC-FO films immersion hydrogenperoxide steam generator after being rinsed 3h is soaked, wherein hydrogenperoxide steam generator
Concentration is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(3) the TFC-FO films after cleaning are taken out, surface washing 5min is carried out using deionized water, hydrochloric acid is then immersed in molten
1h is soaked in liquid, the wherein concentration of hydrochloric acid solution is 0.1% (v/v), and cleaning temperature is 25 DEG C.
(4) TFC-FO after cleaning is placed in 20mM sodium chloride solution, using deionized water as liquid is drawn, carried out
10min backwash, removes the pollutant of film surface residual and the cleaning agent of residual.
After above-mentioned cleaning, TFC-FO films are replaced in operation in AnOMBR devices and obtain following service data：
Initial flux when TFC-FO films after cleaning are run in AnOMBR devices is 7.85LMH, flux fall off rate
For 0.23LMH/d.Rejection to TOC is 98.5%, and the rejection to TP has nearly reached 100%.This and the effect before cleaning
Fruit is the same.This illustrates that the cleaning program can effectively remove the pollutant on FO films surface, recovers the runnability of FO films.
Embodiment 5：Influence of the various concentrations hydrogenperoxide steam generator to the cleaning performance and film properties of FO films
Hydrogenperoxide steam generator that concentration is 0.2%, 0.3%, 0.5%, 1% is respectively adopted to polluting in embodiment 1
TFC-FO films are cleaned, and other steps or parameter are consistent with embodiment 1.
Use 0.2% hydrogen peroxide clean after initial flux of TFC-FO films when being run in AnOMBR devices for
7.27LMH, its flux fall off rate is 0.68LMH/d, and the rejection to TOC is 97.2.%, and the rejection 98% to TP is left
The right side, cleaning performance is preferable；But compared with 0.1% hydrogen peroxide cleaning, flux fall off rate improves 65%, and this is due to
0.2% hydrogen peroxide causes slight membrane damage, and the speed of ion through film accelerates and causes film both sides permeable pressure head to diminish, from
And cause the raising of flux fall off rate.In addition, being existed using the TFC-FO films after 0.3%, 0.5% and 1% hydrogen peroxide cleaning
Initial flux when being run in AnOMBR devices is 7.27LMH, due to the seepage of salt, and flux fall off rate is 1.5LMH/d.This
Illustrate the damage that TFC-FO films are caused during the hydrogen peroxide cleaning using 0.3%, 0.5% and 1%, be not suitable for TFC-FO films
Cleaning.Embodiment 6：Influence of the different hydrogenperoxide steam generator processing times to the cleaning performance and film properties of FO films
Hydrogenperoxide steam generator processing time 1h, 3h, 5h are used respectively, and other steps or parameter are consistent with embodiment 1.
Use 1h and 3h hydrogen peroxide clean after initial flux of TFC-FO films when being run in AnOMBR devices for
7.27LMH, its flux fall off rate is 0.41LMH/d.Rejection to TOC is 98.5%, and the rejection to TP is nearly reached
100%.This is as the effect before cleaning.However, when being 5h between when purged, occurring in that the damage of TFC-FO films, causing
The seepage of salt.Now, initial flux when TFC-FO films are run in AnOMBR devices is 7.27LMH, flux fall off rate
Reach 1.2LMH/d.
Reference examples 1：
Remove in embodiment 1 the step of cleaning using hydrogen peroxide (2), other steps or parameter and embodiment 1
Unanimously.
Initial flux when TFC-FO films after cleaning are run in AnOMBR devices is only 3LMH, is just reached after operation 2d
The end of run (2LMH).This Chemical cleaning of explanation without hydrogen peroxide, can not recover the TFC- of pollution only with physical cleaning
The flux of FO films.
Reference examples 2：
Change the hydrogen peroxide concentration in embodiment 1 into 0.2%, and remove being carried out using hydrochloric acid at collaboration in embodiment 1
The step of reason (3), other steps or parameter are consistent with embodiment 1.
Initial flux when TFC-FO films after cleaning are run in AnOMBR devices is reduction of speed under 7.27LMH, its flux
Rate is 0.82LMH/d, and the rejection to TOC is 97.5%, to TP rejection 98%.With the peroxide of use 0.2% of embodiment 5
The method changed hydrogen solution but employ hydrochloric acid collaboration processing is compared, and the flux fall off rate of film improves 26%.This explanation is double
The mode that oxygen water process is combined with HCl treatment, can act synergistically, and effectively remove pollutant and reduce membrane damage.
Reference examples 3：
The step (4) in embodiment 1 is removed, other steps or parameter are consistent with embodiment 1.
Initial flux when TFC-FO films after cleaning are run in AnOMBR devices is 6.5LMH, and flux fall off rate is
0.35LMH/d.Rejection to TOC is 98.5%, and the rejection to TP has nearly reached 100%.Compared with before cleaning, pollution
The rejection of thing does not change, but the initial flux of TFC-FO films is lower, and flux fall off rate is also bigger.This explanation is in chemistry
The pollutant of residual can further be removed using physics backwash after cleaning.
Although the present invention is disclosed as above with preferred embodiment, it is not limited to the present invention, any to be familiar with this skill
The people of art, without departing from the spirit and scope of the present invention, can do various changes and modification, therefore the protection model of the present invention
Enclose being defined of being defined by claims.
Claims (10)
1. a kind of forward osmosis membrane cleaning method, it is characterised in that including step：
(1) surface washing is carried out with water to the FO films of pollution；
(2) the FO films after flushing are immersed in hydrogenperoxide steam generator；
(3) FO films are taken out from hydrogenperoxide steam generator, then film surface is rinsed with water, be then immersed in hydrochloric acid solution；
(4) FO films are taken out, in immersion sodium chloride solution, backwashed using water as liquid is drawn.
2. according to the method described in claim 1, it is characterised in that the concentration of hydrogenperoxide steam generator is 0.1~0.2% (v/v).
3. according to the method described in claim 1, it is characterised in that be to the washing time that the surface water of the FO films of pollution is rinsed
10~20min.
4. according to the method described in claim 1, it is characterised in that the time of immersion hydrogenperoxide steam generator is 1~3h.
5. according to the method described in claim 1, it is characterised in that the temperature of hydrogenperoxide steam generator is 22~28 DEG C.
6. according to the method described in claim 1, it is characterised in that the time of immersion hydrochloric acid solution is 0.6~1.5h.
7. according to the method described in claim 1, it is characterised in that the concentration of hydrochloric acid solution is 0.8~1.2% (v/v).
8. according to the method described in claim 1, it is characterised in that the temperature of hydrochloric acid solution is 22~28 DEG C.
9. according to the method described in claim 1, it is characterised in that the concentration of sodium chloride solution is 15~25mM.
10. according to the method described in claim 1, it is characterised in that the FO films are the film of polyamide material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110465198A (en) * | 2019-08-21 | 2019-11-19 | 安徽智泓净化科技股份有限公司 | A kind of ultrasonic wave of membrane module is just permeating on-line cleaning method and device |
| CN115041021A (en) * | 2022-05-10 | 2022-09-13 | 天津城建大学 | Molybdenum disulfide composite membrane, and preparation method, cleaning method and application thereof |
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| CN102284249A (en) * | 2011-06-07 | 2011-12-21 | 天津工业大学 | Method and device for cleaning polluted membrane |
| CN102580546A (en) * | 2011-01-10 | 2012-07-18 | 东丽纤维研究所（中国）有限公司 | Method evaluating membrane chemical cleaning recovery performance |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580546A (en) * | 2011-01-10 | 2012-07-18 | 东丽纤维研究所（中国）有限公司 | Method evaluating membrane chemical cleaning recovery performance |
| CN102284249A (en) * | 2011-06-07 | 2011-12-21 | 天津工业大学 | Method and device for cleaning polluted membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110465198A (en) * | 2019-08-21 | 2019-11-19 | 安徽智泓净化科技股份有限公司 | A kind of ultrasonic wave of membrane module is just permeating on-line cleaning method and device |
| CN115041021A (en) * | 2022-05-10 | 2022-09-13 | 天津城建大学 | Molybdenum disulfide composite membrane, and preparation method, cleaning method and application thereof |
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