CN106621831B - A method of it is quickly nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ - Google Patents
A method of it is quickly nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ Download PDFInfo
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- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
Abstract
It is quickly the method for nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ that the present invention, which discloses a kind of, belongs to technical field of membrane separation.Present invention aims to overcome that the deficiency of existing nanofiltration membrane preparation technology, develops a kind of method that simple, cheap, quick nanofiltration membrane is prepared in situ.The present invention, which is utilized without specific condition, to be crosslinking agent with the diamines that graphene oxide reacts, the stickiness of graphene oxide layer is adjusted using the surface tension of water and the collective effect of gas pressure, preparation process is without specially treateds such as heating, drying, in a simple and fast manner, in the device equipped with micro-filtration or ultrafiltration membrane, being prepared in situ for graphene oxide nanofiltration membrane is realized.Method of the invention have many advantages, such as it is low in cost, can be prepared in situ, is renewable and do not limited by basilar memebrane type and shape; prepared nanofiltration membrane water flux with higher; there is good removal effect to ion and organic matter, there is wide scale application prospect.
Description
Technical field
The present invention relates to the methods that micro-filtration or ultrafiltration membrane converted in-situ are quickly nanofiltration membrane by one kind, belong to membrane separation technique
Field.
Background technique
Nanofiltration (NF) be it is a kind of between ultrafiltration and it is reverse osmosis between pressure-driven membrane separation technique, effective filter hole
Diameter is 0.5-2 nanometers.Nanofiltration usually has many advantages, such as that operating pressure is low, and water flux is big, has to inorganic salts and small organic molecule
Certain removal ability has preferable purifying property to coloration and peculiar smell, is widely used in water treatment field.Currently, nanofiltration membrane
Preparation method mainly has phase inversion, blending method, lotus electrochemical process and composite algorithm etc..Wherein composite algorithm is current most commonly used side
Method is by the compound one layer polymer foil preparation with separating property on porous basilar memebrane.It is separation with polymer
There is preferable selectivity and permeability although there is the nanofiltration membrane of active layer, exist and fluorine poisoning easily occurs and easily breeds bacterium etc. to lack
Point, and lead to the decline of performance, the application range of film is subject to certain restrictions.In the side such as the preparation of nanofiltration membrane and separating mechanism research
Face still remains a large amount of technical problems and needs to solve, and needs further to develop cheap, function admirable, the scope of application
Wide nanofiltration membrane.
Graphene oxide is a kind of new carbon haveing excellent performance, and has the characteristics that two-dimensional structure, higher theory compare table
Area and oxygen-containing functional group abundant.Dispersibility of the graphene oxide with machinability more better than graphene and in water,
Various modifications and modulation can be carried out on its surface, be ideal membrane material.The method energy of ultrasound removing is combined using chemical oxidation
Enough a large amount of preparations for realizing graphene oxide solution in inexpensive manner, for graphene oxide membrane scale application provide it is good
Good basis.
Joshi's etc. (Science, 2014,343 (6172): 752-754) the study found that hydrone can be almost without
Frictional force is formed by slit-type structure by graphene sheet layer.Deng (Phys.Chem.Chem.Phys., 2014,
16 (18): 8646-8654) by the method for molecular dynamics simulation, illustrate that theoretically graphene oxide membrane can be realized well
Desalting efficiency and higher water flux.Nair etc. (Science, 2012,335:442-444) utilizes spin-coating method preparation oxidation stone
Black alkene film, and substrate is removed using the method for chemical attack, the fine and close graphene oxide membrane of self-supporting is prepared, is had to vapor
There are the infiltration rate being exceedingly fast, but the film bad mechanical strength of this method preparation, it can not large area preparation.Support type graphene oxide
Film is to have active layer as centrifugation using the graphene oxide layer for being supported on basement membrane surface, utilizes the supporting role of basilar memebrane
Enhance the mechanical strength of film, there is broader practice space.Mi etc. (J.Membrane Sci., 2014,469:80-87) is logical
LBL self-assembly method is crossed, using electrostatic force successively by negatively charged graphene oxide layer and positively charged polypropylene
Nitrile, which loads on basilar memebrane, prepares graphene oxide composite membrane, which needs multiple alternating impregnating load, and operating process is numerous
It is trivial, it is difficult to large-scale production and application.Wang etc. (J.Mater.Chem.A, 2015,3 (8): 4405-4412) is anti-by esterification
It answers, synthesizes the graphene oxide membrane of a series of covalent cross-linking, but cross-linking reaction condition is more harsh, film area is small, it is difficult to
Engineering application.Zhang etc. (J.Membrane Sci., 2016,515:204-211) is by sulfonation in graphene oxide
On piece induces one sulfonic group, and certain reduction treatment has been carried out to graphene oxide solution, utilizes the method preparation of vacuum filtration
The graphene oxide membrane of succinic acid crosslinking, which needs to heat and the catalysis of strong acid condition, and preparation process is complicated, resists
Compression shock ability is poor, limits its further application.
The area that the method for above-mentioned preparation graphene oxide membrane is respectively present such as complex process, film is small, film-strength is low,
Severe reaction conditions are difficult to the problems such as large-scale production.
The Chinese patent of Publication No. 103706264A uses graphene oxide for raw material, and direct filtering prepares graphite oxide
Alkene film, this method do not add any crosslinking agent, and the stability of film does not ensure, it is most likely that leads to the graphene oxide on film
It swells in water, the influence for causing the service life of film to be subject to, while preparation process needs the processing such as drying, is not able to achieve original position
Preparation.The Chinese patent of Publication No. 103736400A uses graphene oxide for raw material, prepares oxidation by the method for coating
Graphene composite film needs to coat basilar memebrane Carboxy Chitosan and heat treatment, and graphene oxide cross-linking reaction needs
It is carried out at a temperature of 60-80 DEG C, preparation process needs the processing such as to coat, heat, dry, and the process is more complicated, is not able to achieve original
Position preparation.The Chinese patent of Publication No. 104028111A uses chemical grafting method, uses graphene oxide for raw material, makes
The sandwich type structural of standby chitosan and graphene oxide, the graft reaction of this method need the special places such as gamma-rays irradiation and drying
Reason, preparation process is complex, is not able to achieve and is prepared in situ.
The above reported article and patent, although using graphene oxide is raw material, the water flux of film is lower, and
And the operations such as heating, drying or gamma-rays irradiation are needed in its preparation process, it is not able to achieve and is prepared in situ, to be difficult to overcome
Possible damage caused by during preparation, transfer, transport, installation of film etc., make the application of graphene oxide nanofiltration membrane by
Certain restrictions.Therefore, be highly desirable to develop it is a kind of it is easy to operate, low in cost, film area is unrestricted, stability is good,
Compression resistance impact, water flux height, good separating effect, can be prepared in situ, be easy to the nanofiltration membrane preparation method of scale application.
Summary of the invention
Barrier it is an object of the invention to overcome above-mentioned the shortcomings of the prior art, across between the preparation and application of film
Hinder, developing one kind can realize that by ultrafiltration or nanofiltration membrane (or device) converted in-situ be to receive in simple, quick, cheap mode
The method of filter membrane (or device).The present invention, which utilizes, to be not necessarily to what any outer plus condition can react with graphene oxide
Diamines is crosslinking agent, using the coefficient compacting step of the capillary force of pressure and water, improves graphene oxide layer
Between cross-linking reaction degree, avoid the adverse effect caused by film properties of traditional drying process, and realize graphene oxide
Film is prepared in situ.Compacting step can be improved the cross-linking reaction degree of film, reduce because of surface graphene film alice or due to bulge
Caused by aggravation concentration polarization the phenomenon that.
The present invention provides a kind of quickly method by micro-filtration ultrafiltration membrane (or device) converted in-situ for nanofiltration membrane (or device),
Include the following steps:
A the release effect of ultrasonic treatment, preparation oxidation stone) are combined by the method for chemical oxidation (improved Hummer method)
Black alkene solution.
B certain reduction treatment) is carried out to graphene oxide solution.
C) respectively prepared and diluted graphene oxide solution and diluted cross-linking agent solution, by by two kinds of solution with certain
Ratio mixing, prepare have be by ultrafiltration or nanofiltration membrane converted in-situ nanofiltration membrane function solution.
D) the above-mentioned mixed solution of certain volume is added in the device equipped with micro-filtration or ultrafiltration basilar memebrane, is made in pressure
Under, make water through basilar memebrane, and graphene oxide sheet is then gradually assembled on basilar memebrane with laminate structure, and is crosslinked
Reaction, forms effective separating layer.Graphite oxide can be controlled by the dosage of function solution, the amount of permeate or filtration time etc.
The thickness and its separating property of alkene film.
E the process being compacted with gas) is carried out to the graphene oxide membrane preliminarily formed, i.e., under conditions of film is wet, is used
Gas applies certain pressure to film (or device) along the direction of filtering and is kept for a period of time, is made using pressure and the capillary of water
Collective effect firmly effectively improves the cross-linking reaction degree between graphene oxide layer, avoids traditional drying process pair
Being prepared in situ for nanofiltration membrane is realized in adverse effect caused by the performance of film.
Method of the invention can also be used in the regeneration of prepared nanofiltration membrane, automatic when passing through film using fluid
Selectivity, the faster position of flow velocity that graphene oxide solution will be had vacant position on automatic preferential filled film, realize the repairing of film with
The regeneration of performance.It can also first be handled with solution, the methods of ultrasonic treatment or physics wiping are by the graphene oxide on basilar memebrane
Layer removal, then with method of the invention be again nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ.
Nanofiltration membrane prepared by method of the invention has operating pressure low, and water flux is big, and it is excellent that water flux conservation rate is good etc.
Point has certain removal ability to inorganic salts and small organic molecule, has preferable purifying property to coloration.Prepared nanofiltration
Film is keeping higher water flux (40kgm under lower pressure (0.8MPa)-2·h-1·MPa-1To 160kgm-2·h-1·MPa-1) while, 23%-42% can be reached to the removal rate of the NaCl of 500mg/L, to the Na of 500mg/L2SO4Go
Except rate reaches 57%-82%, 81%-97% is reached to the methyl orange solution removal rate of 10mg/L.Graphene oxide of the invention
The method that nanofiltration membrane is prepared in situ can effectively avoid pair that may cause during preparation, transfer, transport and installation of film etc.
The damage of film, thus across the obstacle between the preparation and application of graphene oxide nanofiltration membrane.Method of the present invention has
Easy to operate, low in cost, the advantages that film area is unrestricted, stability is good, compression resistance impact, and method is not by substrate
The limitation of film type and form, is film-made thickness and performance is controllable, and film is renewable, has extraordinary adaptability to use condition,
Under relatively low pressure, it is able to maintain higher water flux and salt rejection rate, is had broad application prospects in water treatment field.
Detailed description of the invention
Fig. 1: the cross-section morphology of the scanning electron microscope (SEM) photograph of nanofiltration membrane prepared by the embodiment of the present invention 1；
Fig. 2: the cross-section morphology of the scanning electron microscope (SEM) photograph of nanofiltration membrane prepared by the embodiment of the present invention 2；
Fig. 3: the pure water flux of nanofiltration membrane prepared by the embodiment of the present invention 1 and embodiment 2 changes with time figure.
Specific embodiment
Preparation method of the invention will be described further by specific embodiment below, but the present invention is not limited to
These embodiments.
Embodiment 1
(1) preparation of graphene oxide solution
Graphene oxide solution used in the present invention is to pass through improved Hummer method knot using graphite powder as raw material
Close the release effect preparation of ultrasonic treatment.Its preparation flow is as follows, and 1g graphite powder is put into beaker, 60mL is added into beaker
The concentrated sulfuric acid and 0.5g sodium nitrate.Then under ice-water bath and stirring condition, into said mixture, it is slowly added to 3g high several times
Potassium manganate (KMnO4), whole process temperature is controlled at 20 DEG C or less.After the addition for completing potassium permanganate, it is transferred to 35 DEG C of water
3g potassium permanganate is added in isothermal reaction 10 hours in bath again, continues isothermal reaction 12 hours.After oxidation reaction, in ice
It under conditions of water-bath and stirring, is slowly added to deionized water and causes 500mL, in the process, control temperature is maintained at 20 DEG C or less.
After the completion of dilution, it is 30% hydrogen peroxide (H that about 5mL content, which is added dropwise,2O2) solution, solution colour gradually becomes by brownish red
Glassy yellow.Said mixture is centrifuged, the product after collecting oxidation, and is washed 3 times with the hydrochloric acid of 1:10 (HCl)
Afterwards, it is fitted into bag filter, dialysis is to without other heteroions in deionized water.Product after dialysis is diluted to deionized water
2000mL, and with ultrasonic washing instrument, ultrasonication 3 hours.In the process, the removing to graphene oxide is completed, is obtained
The graphene oxide solution of high degree of dispersion.Usual 1g graphite can prepare about 2g graphene oxide, prepared graphene oxide
Concentration is about 1mg/mL.
(2) reduction treatment of graphene oxide solution
With reference to Zhang etc. (J.Membrane Sci., 2016,515:204-211) method to graphene oxide solution into
Certain reduction treatment is gone.Under relatively mild reducing condition, used by control reaction temperature, reaction time and reducing agent
Amount realizes the partial reduction of graphene oxide solution.Steps are as follows, takes the graphene oxide of 1mg/mL prepared by 100mL molten
Liquid is diluted to 1000mL with deionized water, and is adjusted the pH value of solution to 9-11 with ammonium hydroxide.Then about to the 1000mL
Hydrazine (65wt.%) solution of specific quantity is added in the graphene oxide solution of 0.1mg/mL, the dosage of hydrazine is 0.08mL, is being restored
In step, initial reduction in 2 hours is carried out under conditions of ice-water bath, is subsequently placed in room temperature (25 DEG C) and is continued stirring instead
It answers 24 hours, to prepare the graphene oxide solution of specific reducing degree.
(3) preparation of diamine modified graphene oxide solution
It is used to prepare the diamine modified graphene oxide solution of nanofiltration membrane, is by by treated graphite oxide
It is mixed at a specific ratio after the dilution of alkene solution with certain density butanediamine solution.Steps are as follows, takes that treated
The graphene oxide solution 10mL of 0.1mg/mL, is diluted to 200mL, obtains about 0.005mg/mL treated graphene oxide
Solution.Solution after dilution is ultrasonically treated 10 minutes in ultrasonic washing instrument, to remove, there may be poly- in reduction process
Collection etc. influences, and reaches good dispersion effect.It takes 0.75g butanediamine to be dissolved in 1000mL water, prepares 0.75mg/mL's
Butanediamine solution.It takes the butanediamine solution 1mL of 0.75mg/mL and is diluted to 200mL, it is molten to obtain 0.00375mg/mL butanediamine
Liquid, and stir 10 minutes.Then by above-mentioned 200mL, 0.005mg/mL treated graphene oxide solution, and 200mL,
0.00375mg/mL butanediamine solution is mixed and stirred for uniformly can be used to the preparation of nanofiltration membrane.In this process, due to oxidation
The concentration of graphene solution is very low, can be largely avoided graphene oxide crosslink in advance in the solution reaction and
Reunite.When the graphene oxide of butanediamine modification is gradually assembled on basilar memebrane in the form of laminate, adjacent oxidation stone
Black alkene sector-meeting crosslinks reaction.
It (4) is nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ
Nanofiltration membrane is prepared by basement membranes in situ of micro-filtration or ultrafiltration membrane, is by by prepared diamine modified oxidation stone
Black alkene solution, is added in the test for being equipped with micro-filtration or nanofiltration basilar memebrane or application apparatus, under pressure with filtering
Graphene oxide sheet is assembled on basilar memebrane by method in a manner of laminate, and by being compacted to the film preliminarily formed
Process improve film cross-linking reaction degree and stickiness and complete to prepare.The preparation of nanofiltration membrane is in film test device
It is carried out in Sterlitech HP4750, used basilar memebrane is that Kynoar (PVDF, 0.22um, PVDF, saliva are risen) is micro-
Hole filter membrane, pressure use but are not limited to nitrogen cylinder offer.Steps are as follows, the butanediamine of prepared 400mL from step (3)
In the graphene oxide solution of modification, 25mL is taken to be added in the test for being equipped with micro-filtration or nanofiltration basilar memebrane or application apparatus,
Under the pressure of 0.8MPa, graphene oxide sheet is assembled on the PVDF basilar memebrane installed in advance in a device, to 25mL oxygen
After graphite alkene is filled into completely on PVDF basilar memebrane, provide the pressure of 0.4MPa with gas and keep 30min or so.Due to
The presence of interfacial phenomenon between gas, solid, liquid three-phase, under the collective effect of the capillary force of pressure and water that gas provides,
The spacing of graphene oxide layer is gradually decreased, the cross-linking reaction degree between graphene oxide layer is effectively improved, thus
The graphene oxide layer for realizing graphene oxide sheet, especially surface, preferably fits together, and completes graphene oxide and receives
The preparation of filter membrane.
(5) test and cost explanation for the nanofiltration film properties being prepared in situ
The pressure of film properties test be by but be not limited to high pure nitrogen steel cylinder provide, under 0.8MPa pressure, use deionization
The pure water flux of the prepared nanofiltration membrane of water test, the Na of the NaCl and 500mg/L that are respectively 500mg/L with concentration2SO4Solution
Its desalting performance is tested, tests its removal ability to organic matter with the methyl orange of 10mg/L, the filter area of basilar memebrane is about
1.385×10-3m2.Test result shows that the water flux of nanofiltration membrane one prepared by embodiment 1 is 86.5kgm-2·h-1·
MPa-1, the removal rate to NaCl is 32.9%, to Na2SO4Removal rate be 72.9%, the removal rate to methyl orange is
95.5%.Prepared graphene oxide nanofiltration membrane is during desalination and removal organic matter, water flux and pure water flux
Substantially it keeps identical, during being somebody's turn to do, provides stirring (300 revs/min) condition by hanging on the magneton in device, reduce concentration difference
Polarization.The metering ratio for being 25mL according to treated graphene oxide dosage estimates graphite oxide prepared by 1g graphite
Alkene can be used to prepare about 45m2Graphene oxide nanofiltration membrane, therefore by microfiltration membranes be converted into required for nanofiltration membrane at
This is very low.
Embodiment 2
Nanofiltration membrane two is prepared according to the method for embodiment 1, except that the use of the graphene oxide solution of diamines crosslinking
Amount is 50mL.Nanofiltration membrane two carries out preparation and film properties test on the device described in above-described embodiment 1, with embodiment 2
The water flux of nanofiltration membrane obtained by method is 41.6kgm-2·h-1·MPa-1, the removal rate to NaCl is 42.4%, right
Na2SO4Removal rate be 81.5%, be 96.6% to the removal rate of methyl orange.
Embodiment 3
Nanofiltration membrane three is prepared according to the method for embodiment 1, except that the use of the graphene oxide solution of diamines crosslinking
Amount is 15mL.Nanofiltration membrane three carries out preparation and film properties test on the device described in above-described embodiment 1, the results showed that implement
The water flux of nanofiltration membrane obtained by example 3 is 162.5kgm-2·h-1·MPa-1, the removal rate to NaCl is 22.6%, right
Na2SO4Removal rate be 56.7%, be 80.5% to the removal rate of methyl orange.
Embodiment 1 to 3 the result shows that, can be molten by changing diamine modified graphene oxide with method of the invention
The dosage of liquid adjusts the thickness of graphene oxide membrane, and preparing, there is the graphene oxide of high water flux or preferable separating property to receive
Filter membrane, to meet the needs of different purposes.
Embodiment 4
Nanofiltration membrane four is prepared according to the method for embodiment 1, except that used basilar memebrane is by original poly- inclined fluorine
Vinyl film (PVDF, 0.22um, saliva are risen) is changed to polycarbonate microfiltration membranes (PV, 0.2um, GTTP, Millipore).Nanofiltration membrane
Preparation and film properties test, nanofiltration obtained by the method with embodiment 4 are carried out on four devices described in above-described embodiment 1
The water flux of film is 78.1kgm-2·h-1·MPa-1, the removal rate to NaCl is 30.5%, to Na2SO4Removal rate be
70.3%, the removal rate to methyl orange is 95.1%.
Embodiment 5
Nanofiltration membrane five is prepared according to the method for embodiment 1, except that used basilar memebrane is by original poly- inclined fluorine
Vinyl film (PVDF, 0.22um, saliva are risen) be changed to ultrafiltration membrane (PLBC6210, regenerated cellulose, 3kDa/NMWL,
Millipore).Nanofiltration membrane is fifth is that carry out preparation and film properties test on the device described in above-described embodiment 1, the results showed that
The water flux of nanofiltration membrane obtained by the method for embodiment 5 is 73.9kgm-2·h-1·MPa-1, the removal rate to NaCl is
31.2%, to Na2SO4Removal rate be 72.6%, be 94.6% to the removal rate of methyl orange.
Embodiment 1, embodiment 4 and embodiment 5 the result shows that, method of the invention has extensive adaptability, not by
The limitation of basilar memebrane type, has broad application prospects.
Comparative example 1
Nanofiltration membrane six is prepared according to the method for embodiment 1, except that the pressure not carried out to freshly prepd nanofiltration membrane
Real process.Nanofiltration membrane six carries out preparation and film properties test on the device described in above-described embodiment 1, the results showed that comparative example
The water flux of nanofiltration membrane obtained by 1 is 89.3kgm-2·h-1·MPa-1, the removal rate to NaCl is 6.5%, to Na2SO4
Removal rate be 9.8%, be 25.7% to the removal rate of methyl orange.By the comparison of embodiment 1 and comparative example 1, when lacking this
In inventive method using the capillary force of pressure and water to the compacting process of film when, point of prepared graphene oxide membrane
It is excessively poor from performance.This is because lack compacting process described in 1 step of the embodiment of the present invention (4) in film-forming process, it can not
Phenomena such as what is avoided causes the graphene oxide sheet on prepared film surface layer that alice or bulge occurs, the oxidation stone of stickiness difference
Black alkene layer can play certain bridging effect to the solution being concentrated after separation, separate so that stirring action can not be effectively reduced
Concentration polarization caused by journey, it is very unfavorable to the promotion of graphene oxide nano filter membrane separating property.
Embodiment 1 and comparative example 1 the result shows that, method of the invention utilizes the pressure of gas and the capillary force of water
Collective effect, improve the crosslinking degree and stickiness of graphene oxide film layer, the lamella for improving graphene oxide membrane is (outstanding
It is the lamella on surface layer) desalting ability, concentration polarization adds caused by significantly reducing because of graphene oxide sheet stickiness difference
Acute phenomenon, enhances the separating property of graphene oxide membrane, and realize being prepared in situ for nanofiltration membrane, method of the invention has
Wide application prospect.
The water flux and separating property of nanofiltration membrane prepared by 1 embodiment of the present invention 1 to 5 of table and comparative example 1
Claims (6)
1. a kind of is quickly the method for nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ, which is characterized in that the method is to fill
In the device or element for having micro-filtration or ultrafiltration membrane, with can under conditions of not causing adverse effect to device with graphene oxide
The substance that lamella crosslinks is crosslinking agent, arrives base for graphene oxide-loaded by the method filtered in situ under pressure
On counterdie, and the coefficient compacting process of capillary force of gas pressure and water is combined, i.e., under conditions of film is wet, used
Gas applies certain pressure to film and keeps certain time along the direction of filtering, makees jointly in the capillary force of pressure and water
Under, the spacing of graphene oxide layer is gradually decreased, improve the crosslinking degree and stickiness of graphene oxide membrane, thus real
It by micro-filtration or ultrafiltration membrane or device converted in-situ is quickly now nanofiltration membrane or device.
2. according to claim 1 is quickly the method for nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ, which is characterized in that
The method without heating, drying specially treated, can be realized and be prepared in situ, thus overcome the preparation of film, transfer, transport,
The damage to film that may cause in installation process, the obstacle across between the preparation and application of graphene oxide nanofiltration membrane.
3. according to claim 1 is quickly the method for nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ, which is characterized in that
The method can adapt to the basilar memebrane and its component of various unlike materials or pattern, and the material of basilar memebrane can be macromolecule
Film, inoranic membrane, inorganic/organic hybrid or composite membrane, the shape of basilar memebrane can be plate membrane, tubular membrane, rolled film or hollow
Tunica fibrosa.
4. according to claim 1 is quickly the method for nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ, which is characterized in that
The method is to realize following many advantages by the Macrodilution to graphene oxide solution, increases graphene oxide sheet
The dispersion degree of layer in water effectively avoids agglomeration caused by the graphene oxide sheet and crosslinking agent premature reaction in solution,
Graphene oxide sheet distribution uniformity on basilar memebrane is improved in film-forming process, improving prepared separation has active layer to aoxidize
The stickiness and separating property of graphene film layer.
5. according to claim 1 is quickly the method for nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ, which is characterized in that
The method has recoverability and reproducibility, can be carried out again by method described in claim 1 to the film that performance declines
Secondary repairing and in-situ regeneration can also be handled first with solution, the method for ultrasonic treatment or physics wiping is by the oxidation on basilar memebrane
Graphene layer removal, then with method described in claim 1 be again nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ.
6. according to claim 1 is quickly the method for nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ, which is characterized in that
The film properties of the method preparation are stablized, and the performance with good anti-chlorine, antibacterium and compressive resistance impact can be used extensively
The separation process of liquid phase or gas phase in the energy, chemical industry, pharmacy and field of environment protection.
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| CN107185411A (en) * | 2017-05-19 | 2017-09-22 | 北京理工大学 | It is a kind of in method of the metal cation crosslinking-oxidization graphene nanometer sheet to ultrafiltration membrane modifying |
| CN108939929B (en) * | 2018-08-13 | 2021-06-08 | 清华大学 | Graphene oxide coating modified filter membrane and preparation method and bonding strength evaluation method thereof |
| CN110449039B (en) * | 2019-08-16 | 2021-08-03 | 宁波石墨烯创新中心有限公司 | Graphene/graphene oxide-based separation membrane and preparation method thereof |
| CN110559870A (en) * | 2019-09-21 | 2019-12-13 | 盐城增材科技有限公司 | Functionalized graphene/polyaniline composite filtering membrane and preparation method thereof |
| CN111013412B (en) * | 2019-12-31 | 2021-10-15 | 西南石油大学 | Preparation method of polypyrrole microsphere hybridized graphene oxide nanofiltration membrane |
| CN114432909A (en) * | 2022-01-30 | 2022-05-06 | 大连理工大学 | High-stability ceramic-based sub-nanopore graphene composite membrane and precise separation application |
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| US20130075326A1 (en) * | 2011-09-27 | 2013-03-28 | Electronics And Telecommunications Research Institute | Filter fabrication method and the filter formed thereby |
| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| CN103240007A (en) * | 2013-05-13 | 2013-08-14 | 嵇天浩 | Method for preparing graphene-oxide-filled microfiltration composite material |
| CN106000121A (en) * | 2016-06-22 | 2016-10-12 | 清华大学 | Solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and preparation method thereof |
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