CN110141978A - A kind of ultra-thin composite membrane and preparation method thereof - Google Patents
A kind of ultra-thin composite membrane and preparation method thereof Download PDFInfo
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a kind of using graphene quantum dot as ultra-thin composite membrane of middle layer and preparation method thereof；Described includes addition graphene quantum dot middle layer step, interface polymerization reaction step, chemical crosslinking step and activating solvent step by the preparation step of the ultra-thin composite membrane of middle layer of graphene quantum dot；The present invention improves the separating property of film by addition graphene quantum dot middle layer significantly；The graphene quantum dot reduces aperture, is conducive to interface polymerization reaction, to effectively improve the separating property of film due to that can increase the hydrophily of basement membrane with great amount of hydroxy group and carboxyl；Preparation process of the present invention is simple, has a good application prospect in organic solution system separation field.
Description
Technical field
The invention belongs to technical field of membrane separation, and in particular to a kind of ultra-thin composite membrane and preparation method thereof.
Background technique
Sea water desalination membrane technology can remove macromolecular, colloid, protein, the particle etc. in solution, have it is low using pressure,
The characteristics of water yield is big, convenient for operation, the film being related to has reverse osmosis and nanofiltration membrane etc..Reverse osmosis membrane is most fine one kind
UF membrane product, all dissolution salts of energy effectively catching and molecular weight are greater than 100 organic matter, while allowing hydrone logical
It crosses.Nanofiltration (NF) is a kind of membrane separation technique between ultrafiltration (UF) and reverse osmosis (RO), and be otherwise known as " loose type reverse osmosis
Thoroughly ", with ultrafiltration and reverse osmosis identical, nanofiltration membrane is also with pressure-actuated membrane separation technique.The nanofiltration of water solution system application
The deficiency between ultrafiltration membrane and reverse osmosis membrane has been filled up in the appearance of film, and it is saturating to show good selection to the ion of different valence state
The property crossed, the organic matter to divalent ion, multivalent ion and molecular weight greater than 200Da have preferable removal effect.By to seawater
The exploitation and industrialization of reverse-osmosis membrane element needed for desalination and nanofiltration membrane component, achievement are also widely applied to surface water
The fields such as purified treatment, special separation, wastewater treatment, municipal middle water or recycling sewage generated by making, coverage is more than sea water desalination
Want significantly more expansive, market demand is also bigger.
Mainly application concentrates on water solution system for nanofiltration, shows good selection to the ion of different valence state and penetrates
Property, the organic matter to divalent ion, multivalent ion and molecular weight greater than 200Da has preferable removal effect.
Currently, a large amount of organic solvents are widely used in paint, medicine, papermaking, chemical industry, petroleum and petrochemical industry, printing, weaving
In equal fields, and it is usually not small for the usage amount of organic solvent in the industrial production.Common organic solvent have toluene,
Alcohols (methanol, ethyl alcohol, isopropanol), esters, ketone (acetone, cyclohexanone, methyl ethyl ketone, N-Methyl pyrrolidone), acetonitrile,
Ethyl acetate, dimethylformamide, aromatic hydrocarbons, halogenated hydrocarbon etc., it is all noxious material that these are most of, and is much all proved
With very strong carcinogenic nature, therefore how more effectively to reuse organic solvent and seem and be even more important.In organic solvent body
Tradition process for separating and purifying such as rectifying, extraction, crystallization etc. used in system, it is complicated for operation, energy consumption is higher, and traditional handicraft is very
Hardly possible automation, operator and make staff bring health hazard often in contact with organic solvent is arrived.Nanofiltration process has room temperature
Separation produces the features such as simple without inversion of phases, operation and amplification, has in fields such as petrochemical industry, medicine, food, fine chemistry industries
There is great Exploitative potential.The nanofiltration membrane major applications being commercialized at present are received in water solution system, the commodity of organic solvent-resistant
Filter membrane is considerably less, and solvent resistance when applying in practical organic solvent system is poor, and phase inversion polyimides is resistance to
Solvent nanofiltration membrane flux is lower.
In recent years, with the rapid development of nanotechnology, some functional inorganic nano material in-situs are introduced into polymer
An important research direction is had evolved into permselective property and the anti-pollution stability etc. that improve film in film.Some researchs
Person also considers that the mode for introducing nano particle middle layer improves the separating property of film.Such as Wu (Journal of Membrane
Science, 515 (2016) 238-244) it is thin by being added between micro-filtration film support and the dense layer surface of interfacial polymerization
Hydrophily multi-walled carbon nanotube (MWCNTs) middle layer is prepared for a kind of novel thin film composite nanometer filtering film, thin with ultrafiltration membrane support
Film composite nanometer filtering film is compared, which shows up to 105.4 5.9 ± 1.8Lm in 0.6MPa-2·h-1Water flux (make
The flux doubles of traditional flux) and to Na2SO4High rejection (~95%).
Graphene quantum dot (GQDs) is a kind of novel quasi-zero dimension nano material, is nanoscale graphene film, not only
With stronger quantum effect, boundary effect and fluorescence property, and have good thermal stability and chemical stability and
Excellent biocompatibility and hypotoxicity.GQDs contains a large amount of oxygen-containing functional group, such as hydroxyl, carboxyl and epoxy due to its surface
Base can interact with matrix, be the hot spot of Recent study.Current research is mostly suitable for water solution system
Composite membrane.Based on the property of GQDs itself, a kind of composite hybridization film with stabilized flux and higher rejection is developed, by it
It applies in the separation of organic solvent system water solution system, there is good application value.
Summary of the invention
The present invention lower, film not anti-pollution for flux in the prior art towards water solution system nanofiltration and reverse osmosis membrane
The technical issues of, and the nanofiltration membrane poor solvent resistance towards organic solvent system, phase inversion polyimides solvent resistant nanofiltration membrane
The lower technical problem of flux proposes that a kind of ultra-thin composite membrane, preparation method and applications, prepared ultra-thin composite membrane have
Good separating property.
To achieve the above object, technical scheme is as follows.
The first aspect of the present invention discloses a kind of ultra-thin composite membrane, by depositing one layer in ultrafiltration or micro-filtration membrane surface
Nano material middle layer, formed in nanometer middle layer using interfacial polymerization one layer of selective separating be made, in which:
(1) the nano material middle layer described in is made of graphene quantum dot (GQDs)；The GQDs includes amino graphite
Alkene quantum dot, carboxylated graphene quantum dot；
(2) the average piece diameter of the GQDs described in is less than or equal to 30nm；Preferably, the average piece diameter of the GQDs is less than or waits
In 20nm；It is furthermore preferred that the average piece diameter of the GQDs is less than or equal to 10nm；
(3) average thickness of the GQDs described in is less than or equal to 5nm；Preferably, the average thickness of the GQDs is less than or waits
In 2nm；
(4) the GQDs nano material middle layer described in is modified on basement membrane by the following method: first by basement membrane and coating material
After solution contacts 10s~30min, remove surface modification agent solution remained on surface, and after drying, then abundant with GQDs suspension
1~300s is contacted, removes the GQDs suspension of excess surface, then dry, GQDs nano material middle layer is modified onto basement membrane；
Preferably, the coating material includes polyethyleneimine；
(5) the GQDs suspension described in is aqueous solution, and wherein the concentration range of GQDs is 1~500mg/L；
(6) average thickness of the GQDs nano material middle layer described in is less than 10nm；Preferably, in the GQDs nano material
The average thickness of interbed is less than 5nm；
(7) average thickness of the selective separating described in is less than 30nm, and mean roughness is less than 5nm.
Preferably, a kind of ultra-thin composite membrane is the nanofiltration membrane applied towards organic solvent system, has following spy
Sign:
(1) basement membrane described in, which contains, to crosslink the acyl reacted with aliphatic polybasic amine compounds or aromatic polycarboxylic amine compounds
Imine group；
(2) selective separating described in is polyamide；
(3) by being covalently keyed between the basement membrane and the GQDs nano material middle layer described in；
(4) by being covalently keyed between the GQDs nano material middle layer and the separating layer described in；
(5) the ultra-thin composite membrane after the interfacial polymerization described in utilizes aliphatic polybasic amine compounds or aromatic polycarboxylic amine compounds
Carry out whole crosslinking；
(6) film after whole crosslinking described in passes through the processing of aprotic, polar type activating solvent again.
Preferably, the ultra-thin composite membrane of a kind of solvent resistant, which is characterized in that the ultra-thin composite membrane at 25 DEG C and
Under transmembrane pressure 1.0MPa, to 100mgL-1The rejection of rhodamine B in rhodamine B ethanol solution is greater than 98%, and flux is big
In 40Lm-2·h-1, the molecular weight of the rhodamine B is 479 dalton.
The second aspect of the present invention discloses a kind of preparation method of ultra-thin composite membrane.The following steps are included:
Step 1: after membrane surface and surface modification agent solution contact 10s~30min, the remaining surface of membrane surface is removed
Agent solution is modified, basement membrane is dried, then after coming into full contact with 1~300s with GQDs suspension, the extra GQDs of removal membrane surface
Suspension dries, the basement membrane after being modified；
Step 2: the membrane surface after modification that step 1 obtains is filled with the aqueous phase monomers solution containing aromatic diamine compound
After tap touching 1s~120s, removes the aqueous phase monomers solution of film surface and dry；By the film surface after drying and contain aromatic series
After the solution (organic phase monomer solution) of first organic solvent of polynary acyl chlorides comes into full contact with 1s~120s, remove film surface has
Machine phase monomer solution, after film is heat-treated 10s~300s at a certain temperature, is cooled to room temperature in a dry environment, obtains
Hybridization compounding film containing GQDs middle layer；
Preferably, a kind of preparation method of ultra-thin compound solvent resistant film, further includes following steps:
Step 3: the cross-linking agent solution crosslinking one by the hybridization compounding film containing GQDs middle layer of step 2 Jing Guo certain temperature
After fixing time, film surface is rinsed with the second organic solvent to get the crosslinking hybrid composite membrane containing GQDs middle layer is arrived；
Step 4: the activating solvent activation by the crosslinking hybrid composite membrane containing GQDs middle layer of step 3 Jing Guo certain temperature
Processing after a certain period of time, is dried, and is replaced with third organic solvent, is then stored in third organic solvent, obtains ultra-thin compound
Film.
Preferably, contain in the aqueous phase monomers solution: aromatic diamine compound.
Preferably, the aromatic diamine compound includes the virtue of m-phenylene diamine (MPD), p-phenylenediamine, other amidos containing there are two
The combination of aroma compounds or above-mentioned any more persons.
Preferably, the mass percent concentration range of the aromatic diamine compound is 0.01%~4.0%.
Preferably, contain in the organic phase monomer solution: fragrant ternary acyl chlorides or mixing aromatic polycarboxylic acyl chlorides and the
One organic solvent.
Preferably, the aromatic polyvalent acyl chlorides includes 1,3,5- pyromellitic trimethylsilyl chlorides, and mixing aromatic polycarboxylic acyl chlorides is
The combination of fragrant ternary acyl chlorides and four formyl chloride of 1,2,4,5- benzene or other aromatic polycarboxylic acyl chlorides.
Preferably, contain in the cross-linking agent solution: one or more crosslinking agents and the second organic solvent.
Or mixtures thereof preferably, the crosslinking agent includes aromatic diamine compound, aliphatic diamine compound,.
Preferably, the aliphatic diamine compound includes the fat of ethylenediamine, hexamethylene diamine, other amidos containing there are two
The combination of compounds of group or above-mentioned any more persons.
Preferably, the crosslinking agent is ethylenediamine or hexamethylene diamine.
Preferably, the activating solvent includes n,N-Dimethylformamide (DMF), N-Methyl pyrrolidone (NMP), two
Methylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or above-mentioned any a variety of combination.
Preferably, first organic solvent includes the hydro carbons such as alkane and other nonpolarity and weak polar solvent.
Preferably, second organic solvent includes isopropanol.
Preferably, the third organic solvent includes ethyl alcohol.
Preferably, the crosslinking temperature range is bubble point temperature of the room temperature to cross-linking agent solution, the crosslinking time
For 5min~4h.
Preferably, the active temperature range is bubble point temperature of the room temperature to activating reagent, and the activation time is
5min~120min.
Preferably, the mass percent concentration range of the fragrant ternary acyl chlorides is 0.005%~1.0%.
Preferably, the mass percent concentration range of the crosslinking agent is 1.0%~20.0%.
The third aspect of the invention discloses a kind of application of ultra-thin composite membrane, which is characterized in that is used for organic solvent
System isolation and purification and water solution system isolation and purification, and aqueous simultaneously and organic solvent solution system solute with
The isolation and purification of solvent, wherein the molecular weight ranges of solute are 200~1000 dalton；
Technical solution of the present invention achieves significant technical effect and progress, has substantive distinguishing features.
The preparation method of ultra-thin composite membrane of the present invention, by depositing GQDs in ultrafiltration or micro-filtration basement membrane, then into
The method of row interfacial polymerization improves the separating property and solvent resistance of film, and by chemical crosslinking and activating solvent step, greatly
The big stability and separating property for improving film, while having expanded the application system of nanofiltration membrane.
Of the invention one is significant, and technological merit is, it is a kind of novel that GQDs nano material is deposited in polyimide base film
Quasi-zero dimension nano material, be nanoscale graphene film, not only have stronger quantum effect, boundary effect and fluorescence
Can, and there is good thermal stability and chemical stability and excellent biocompatibility and hypotoxicity.Due to its surface
Containing a large amount of oxygen-containing functional group, such as hydroxyl, carboxyl and epoxy group improve the hydrophily of basement membrane, are conducive to interfacial polymerization
Journey controls the process of interfacial polymerization, thinner separating layer can be obtained, to improve the flux of film.
The significant technological merit of of the invention second is that the concentration of aqueous phase monomers and oil phase monomer is all very low, generation
Separating layer is very thin, reduces the flow resistance of solvent, improves flux.
The significant technological merit of third of the invention is, effective by carrying out chemical crosslinking step after interfacial polymerization
The solvent resistance of ground raising film.Using post-crosslinking, crosslinking agent and polyimide-based film reaction form more solvent-proof polyamide；Also
Diamine compound and GQDs middle layer in aqueous phase monomers solution can be made to form amide covalent bond, increase separating layer and GQDs layers
Between effect；The Surface Modification Effect can also be played with free acyl chloride reaction, have very big mention to the separating property of film
It is high.
The significant technological merit of of the invention the 4th is handled by further activating solvent, will be a small amount of uncrosslinked
Small molecular weight polymer dissolution is removed, and the steric configuration of adjust automatically and optimization polymer, makes polymer molecule space structure
The energy of type is lower, and polymer space pore structure more evenly, to further improve the flux and rejection of film, is kept simultaneously
The chemistry and mechanical stability of film.
Through the above technical innovation, the present invention achieves significant technological progress, in salt-water system, separation water middle-molecular-weihydroxyethyl
Range is the organic matter of 200~2000 dalton and organic solution system separates and the water treatment field containing organic solvent has
Fabulous application prospect.
Specific embodiment
Below by specific comparative example and embodiment, the present invention will be further described.
Aromatic diamine compound used is m-phenylene diamine (MPD) (MPD)；
Fragrance ternary acyl chlorides used is 1,3,5- pyromellitic trimethylsilyl chloride (TMC)；
Coating material used is polyethyleneimine (PEI)；
Basement membrane crosslinking agent used is hexamethylene diamine；
First organic solvent is n-hexane；
Second organic solvent is isopropanol；
Third organic solvent is ethyl alcohol；
Activating solvent is N,N-dimethylformamide (DMF)；
Under 25 DEG C and transmembrane pressure 1.0MPa, with 100mgL-1Rhodamine B (479 dalton)-ethanol solution measure institute
The rejection of the film of preparation and corresponding solvent flux.
Comparative example 1:
Basement membrane is polyimides (PI) flat plate ultrafiltration membrane, molecular weight 50000Da；
The aromatic diamine compound is dissolved in deionized water, it is molten to be made into aqueous phase monomers for mass percent concentration 0.1%
Liquid.
The fragrant ternary acyl chlorides is dissolved in the first organic solvent, mass percent concentration 0.005% is made into organic
Phase monomer solution.
The film step and condition of polyamide composite nanofiltration membrane are as follows:
After membrane surface and aqueous phase monomers solution are come into full contact with 120s, remove the aqueous phase monomers solution of membrane surface, in room temperature
Air in naturally dry remove film surface after the membrane surface after drying and organic phase monomer solution are come into full contact with 60s
Film is put into rapidly in 80 DEG C of drying box and dries 5min by organic phase monomer solution, after taking-up in dry environment natural cooling,
Obtain dry state polyamide composite nanofiltration membrane.
Obtained dry state nanofiltration membrane is put into the cross-linking agent solution that mass percent concentration is 10%, temperature is 60 DEG C and is handed over
To get the nanofiltration membrane for arriving crosslinking after connection 30min；Nanofiltration membrane is put into again in 80 DEG C of activating reagent DMF and activates 30min, that is, made
Obtain polyamide composite nanofiltration membrane.
Prepared polyamide composite nanofiltration membrane uses 100mgL under 25 DEG C and transmembrane pressure 1.0MPa-1Luo Dan
Bright B- ethanol solution carries out separating property test.The rejection of rhodamine B is 87.4%, and ethyl alcohol flux is 31.0Lm-2·h-1(being abbreviated as LMH), rejection is not high, illustrates that prepared film defect is more.
Embodiment 1
It is 100mgL by concentration-1GQDs aqueous solution ultrasound 60min, it is spare.The average piece diameter thickness of the GQDs
1.8nm；The average thickness 1.9nm of the GQDs.
Steps are as follows for film:
Step 1: after the polyethylenimine solution that basement membrane and concentration are 0.005wt% is come into full contact with 30s at 25 DEG C, remove
The remaining dressing agent of membrane surface and after drying comes into full contact with 60s with GQDs aqueous solution, the free suspension of removal film surface,
Dry the hybridized film modified；
Step 2: after the hybridized film for the modification that step 1 obtains and aqueous phase monomers solution are come into full contact with 120s, remove basement membrane table
The aqueous phase monomers solution in face simultaneously dries 45s；Film after drying and organic phase monomer solution are come into full contact with into 60s, remove film surface
Organic phase monomer solution is heat-treated 5min in the atmosphere in 80 DEG C, puts after taking-up and be cooled to room temperature in a dry environment, obtain
To the dry state composite membrane containing GQDs middle layer；
Step 3: step 2 obtained into the dry state composite membrane containing GQDs middle layer be put into crosslinking agent quality percent concentration be
10%, the hybridization compounding containing GQDs middle layer that crosslinking is arrived after 30min is crosslinked in the cross-linking agent solution that temperature is 60 DEG C
Nanofiltration membrane；
Step 4: the composite nanometer filtering film containing GQDs middle layer of obtained crosslinking is put into 80 DEG C of activating reagent DMF living
Change 30min.
Test condition is identical as comparative example 1.
The average thickness of the selective separating is 45nm, mean roughness 2.37nm.
Prepared ultra-thin composite nanometer filtering film is 94% to the rejection of rhodamine B, is higher than comparative example, illustrates drawing for GQDs
Enter to can control interfacial polymerization process, improves the separating property of film.
Embodiment 2
The difference from embodiment 1 is that: polyimide base film is filled at 25 DEG C with 0.025wt% polyethyleneimine in step 1
Tap touching 30s.
Other all steps are same as Example 1；
Test condition is identical as comparative example 1.
Prepared multi-functional hybridization compounding nanofiltration membrane is 98.2% to the rejection of rhodamine B, and the flux of ethyl alcohol is
33.8 LMH are much higher than comparative example.
Embodiment 3
Be with the difference of embodiment 2: polyimides concentration used in step 1 is 0.05wt%.
Other all steps are same as Example 1.
Test condition is identical as comparative example 1.
The average thickness of the selective separating is 25nm, and mean roughness is less than 2.0nm.
Prepared ultra-thin composite nanometer filtering film is 98.4% to the rejection of rhodamine B, and the flux of ethyl alcohol is 40.2LMH,
Much higher than comparative example.
Prepared multi-functional hybridization compounding nanofiltration membrane is impregnated 8 days in 80 DEG C of DMF, and the flux of ethyl alcohol is 51.7
LMH, the rejection of rhodamine B are 98.3%.Illustrate that prepared multi-functional hybridization compounding nanofiltration membrane has good solvent resistance
Energy.
Embodiment 4
Be with the difference of embodiment 3: graphene quantum dot concentration used in step 1 is 5mgL-1。
Other all steps are same as Example 1.
Test condition is identical as comparative example 1.
Prepared ultra-thin composite nanometer filtering film is 99.2% to the rejection of rhodamine B, and the flux of ethyl alcohol is 21.3LMH.
Embodiment 5
Be with the difference of embodiment 3: graphene quantum dot concentration used in step 1 is 200mgL-1。
Other all steps are same as Example 1.
Test condition is identical as comparative example 1.
Prepared ultra-thin composite nanometer filtering film is 96.4% to the rejection of rhodamine B, and the flux of ethyl alcohol is 40.8LMH,
Much higher than comparative example 1.
Comparative example 2:
Basement membrane is polysulfones (PSF) flat plate ultrafiltration membrane, molecular weight 80000Da.
The piperazine is dissolved in deionized water, mass percent concentration 0.5% is made into aqueous phase monomers solution.
The fragrant ternary acyl chlorides is dissolved in the first organic solvent, mass percent concentration 0.1% is made into organic phase
Monomer solution.
The film step and condition of polyamide composite nanofiltration membrane are as follows:
After membrane surface and aqueous phase monomers solution are come into full contact with 60s, remove the aqueous phase monomers solution of membrane surface, in room temperature
Naturally dry in air, after the membrane surface after drying and organic phase monomer solution are come into full contact with 30s, that removes film surface has
Film is put into rapidly in 80 DEG C of drying box and dries 7min by machine phase monomer solution, after taking-up in dry environment natural cooling, obtain
To dry state polypiperazine-amide composite nanometer filtering film.
Prepared polypiperazine-amide composite nanometer filtering film is under 25 DEG C and transmembrane pressure 1.0MPa, to 2000mgL-1's
Na2SO4Aqueous solution carries out separating property test.
Na2SO4Rejection be 95.83%, water flux 68.67LMH.
Embodiment 6
It is 100mgL by concentration-1GQDs aqueous solution ultrasound 60min, it is spare.The average piece diameter 3.0nm of GQDs, average thickness
2.0nm。
Steps are as follows for film:
Step 1: it after the polyethylenimine solution that PSF basement membrane and concentration are 0.025wt% is come into full contact with 30s at 25 DEG C, goes
After falling the remaining dressing agent of membrane surface and drying, 60s, the free suspension of removal film surface are come into full contact with GQDs aqueous solution
Liquid dries the hybridized film modified；
Step 2: after the hybridized film for the modification that step 1 obtains and aqueous phase monomers solution are come into full contact with 60s, remove membrane surface
Aqueous phase monomers solution and dry 45s；Film after drying and organic phase monomer solution are come into full contact with into 30s, removing film surface has
Machine phase monomer solution is heat-treated 7min in the atmosphere in 80 DEG C, puts after taking-up and be cooled to room temperature in a dry environment, obtain
Dry state composite nanometer filtering film containing GQDs middle layer；
Test condition is identical as comparative example 2.
Prepared polypiperazine-amide composite nanometer filtering film Na2SO4Rejection be 95.56%, water flux 90.61LMH.
Embodiment 7
It is with the difference of embodiment 6: comes into full contact with polysulfones basement membrane at 25 DEG C with 0.05wt% polyethyleneimine in step 1
30s。
Other all steps are same as Example 6.
Test condition is identical as comparative example 1.
Prepared polypiperazine-amide composite nanometer filtering film Na2SO4Rejection be 95.86%, water flux 88.79LMH.
Embodiment 8
It is with the difference of embodiment 6: comes into full contact with polysulfones basement membrane at 25 DEG C with 0.1wt% polyethyleneimine in step 1
30s.Other all steps are same as Example 6.
Test condition is identical as comparative example 2.
Prepared polypiperazine-amide composite nanometer filtering film Na2SO4Rejection be 96.26%, water flux 72.69LMH.
The comparison of the atomic force microscope and scanning electron microscope image of ultra-thin composite nanometer filtering film and traditional solvent resistant nanofiltration membrane, film
Surface become more smooth, illustrate that interfacial polymerization process has obtained effective control, form more even curface, more added with
Conducive to passing through for solvent, the anti-fouling performance of film is improved.
Pore analysis the result shows that, prepared ultra-thin composite nanometer filter membrane aperture reduces, and the rejection for resulting in film increases；
Meanwhile hole density and porosity also increase considerably, and result in dramatically increasing for flux.
I.e. the present invention achieves significant technical effect and progress.
By the separating property of composite nanometer filtering film prepared by the polyamide composite nanofiltration membrane of comparative example 1 and 2 and each embodiment
With the comparison of solvent resistance, the results are shown in Table 1.Comparative example 1 and the ultra-thin composite nanometer filtering film of Examples 1 to 5 preparation pass through
The DMF activation 30min for crossing 60 DEG C of 30min and 80 DEG C of hexamethylene diamine crosslinking, is tested to rhodamine B-ethanol solution separation property
Can, test condition and comparative example 1 are all the same.Ultra-thin composite nanometer filtering film prepared by comparative example 2 and embodiment 6~8 is without oneself
Diamines crosslinking and DMF activation, are tested to rhodamine B-ethanol solution separating property, test condition and comparative example 2 are all the same.
The separating property comparison of 1 pair of example of table and the composite nanometer filtering film of embodiment preparation
As shown in Table 1, the film of comparative example 1 is very low to the rejection of rhodamine B, is because of the separating layer that interfacial polymerization process generates
Defect is more.
Embodiment covers one layer of GQDs, increases membrane surface hydrophily and porosity, subtract compared with comparative example on basement membrane
Small basement membrane aperture is conducive to the process of control interface polymerization, keeps the separation layer defects generated few, while separating layer is relatively thin, leads to
Amount and rejection all significantly improve.
Above embodiments explanation, one layer of GQDs middle layer is applied on basement membrane, is had a great impact to interfacial polymerization process, institute
The ultra-thin composite membrane of preparation has excellent performance, achieves significant technical effect and progress.
It should be pointed out that above-described embodiment is only currently preferred specific embodiment, do not constitute to this
In protection scope of the present invention that the limitation of invention, any feature for falling into the claims in the present invention or equivalent feature are constituted
Embodiment, which is constituted, invades patent right of the invention.
Claims (25)
1. a kind of ultra-thin composite membrane, by depositing one layer of nano material middle layer, using boundary in ultrafiltration or micro-filtration membrane surface
Face is aggregated in one layer of selective separating of formation in nanometer middle layer and is made, which is characterized in that
The nano material middle layer is made of graphene quantum dot (GQDs)；The GQDs includes amination graphene amount
Sub- point；
The average piece diameter of the GQDs is less than or equal to 30nm；Preferably, the average piece diameter of the GQDs is less than or equal to
20nm；It is furthermore preferred that the average piece diameter of the GQDs is less than or equal to 10nm；
The average thickness of the GQDs is less than or equal to 5nm；Preferably, the average thickness of the GQDs is less than or equal to
2nm；
The GQDs nano material middle layer is modified on basement membrane by the following method: first by basement membrane and surface modification agent solution
After contacting 10s~30min, remove surface modification agent solution remained on surface, and after drying, then come into full contact with GQDs suspension
1~300s, removes the GQDs suspension of excess surface, then dries, and GQDs nano material middle layer is modified onto basement membrane；
Preferably, the coating material includes polyethyleneimine；
The GQDs suspension is aqueous solution, and wherein the concentration of GQDs is 1~500mg/L；
The average thickness of the GQDs nano material middle layer is less than 10nm；Preferably, among the GQDs nano material
The average thickness of layer is less than 5nm；
The average thickness of the selective separating is less than 30nm, and mean roughness is less than 2nm.
2. a kind of ultra-thin composite membrane according to claim 1, which is characterized in that
Pass through model ylid bloom action power or hydrogen bond or covalent bond between the GQDs nano material middle layer and the separating layer
Connection.
3. a kind of ultra-thin composite membrane according to claim 1, which is characterized in that the selective separating is polyamide.
4. a kind of ultra-thin composite membrane according to claim 1, which is characterized in that
A kind of ultra-thin composite membrane is solvent resistant composite membrane；
It is sub- that the basement membrane contains the acyl that can be crosslinked and react with aliphatic polybasic amine compounds or aromatic polycarboxylic amine compounds
Amine groups；
By being covalently keyed between the basement membrane and the GQDs nano material middle layer；
By being covalently keyed between the GQDs nano material middle layer and the separating layer；
Ultra-thin composite membrane after the interfacial polymerization using aliphatic polybasic amine compounds or aromatic polycarboxylic amine compounds into
The whole crosslinking of row；
Film after the whole crosslinking passes through the processing of aprotic, polar type activating solvent again.
5. a kind of ultra-thin composite membrane according to claim 2, which is characterized in that the ultra-thin composite membrane at 25 DEG C and across
Under membrane pressure difference 1.0MPa, to 100mgL-1The rejection of rhodamine B in rhodamine B ethanol solution is greater than 98%, and flux is greater than
40L·m-2·h-1, the molecular weight of the rhodamine B is 479 dalton.
6. a kind of preparation method of ultra-thin composite membrane, which comprises the following steps:
Step 1: after membrane surface and surface modification agent solution contact 10s~30min, the remaining surface of membrane surface is removed
Agent solution is modified, basement membrane is dried, then after coming into full contact with 1~300s with GQDs suspension, the extra GQDs of removal membrane surface
Suspension dries, the basement membrane after being modified；
Step 2: the membrane surface after modification that step 1 obtains is filled with the aqueous phase monomers solution containing aromatic diamine compound
After tap touching 1s~120s, removes the aqueous phase monomers solution of film surface and dry；By the film surface after drying and contain aromatic series
After the solution of first organic solvent of polynary acyl chlorides comes into full contact with 1s~120s, the organic phase monomer solution of film surface is removed, it will
It after film is heat-treated 10s~300s at a certain temperature, is cooled to room temperature, is obtained containing GQDs middle layer in a dry environment
Hybridization compounding film.
7. a kind of preparation method of ultra-thin composite membrane according to claim 6, which is characterized in that the ultra-thin composite membrane
Also pass through following processing step:
Step 3: the crosslinking agent of hybridization compounding film Jing Guo certain temperature as claimed in claim 6 containing GQDs middle layer is molten
Liquid is crosslinked after a certain period of time, rinses film surface with the second organic solvent to get the crosslinking hybrid composite membrane containing GQDs middle layer is arrived；
Step 4: the activating solvent activation by the crosslinking hybrid composite membrane containing GQDs middle layer of step 3 Jing Guo certain temperature
Processing after a certain period of time, is dried, and is replaced with third organic solvent, is then stored in third organic solvent, obtains ultra-thin compound
Film.
8. a kind of preparation method of ultra-thin composite membrane according to claim 6 or 7, which is characterized in that the water phase list
Contain in liquid solution: aromatic diamine compound.
9. a kind of preparation method of ultra-thin composite membrane according to claim 8, which is characterized in that the aromatic diamines
Closing object includes m-phenylene diamine (MPD), p-phenylenediamine, the aromatic compound of other amidos containing there are two or the combination of above-mentioned any more persons.
10. a kind of preparation method of ultra-thin composite membrane according to claim 8, the quality of the aromatic diamine compound
Percent concentration range is 0.01%~4.0%.
11. a kind of preparation method of ultra-thin composite membrane according to claim 6 or 7, which is characterized in that the organic phase
Contain in monomer solution: fragrant ternary acyl chlorides or mixing aromatic polycarboxylic acyl chlorides and the first organic solvent.
12. a kind of preparation method of ultra-thin composite membrane according to claim 6 or 7, which is characterized in that the aromatic series
Polynary acyl chlorides includes 1,3,5- pyromellitic trimethylsilyl chlorides, and mixing aromatic polycarboxylic acyl chlorides is fragrant ternary acyl chlorides and 1,2,4,5- benzene tetramethyls
The combination of acyl chlorides or other aromatic polycarboxylic acyl chlorides.
13. a kind of preparation method of ultra-thin composite membrane according to claim 7, which is characterized in that the crosslinking agent is molten
Contain in liquid: one or more crosslinking agents and the second organic solvent.
14. a kind of preparation method of ultra-thin composite membrane according to claim 7, which is characterized in that the crosslinking agent packet
Or mixtures thereof aromatic diamine compound, aliphatic diamine compound are included,.
15. a kind of preparation method of ultra-thin composite membrane according to claim 14, which is characterized in that the aliphatic two
Amine compounds include ethylenediamine, hexamethylene diamine, the aliphatic compound of other amidos containing there are two or the group of above-mentioned any more persons
It closes.
16. a kind of preparation method of ultra-thin composite membrane according to claim 15, which is characterized in that the crosslinking agent is
Ethylenediamine or hexamethylene diamine.
17. a kind of preparation method of ultra-thin composite membrane according to claim 7, which is characterized in that the activating solvent
Including N,N-dimethylformamide (DMF), N-Methyl pyrrolidone (NMP), dimethyl acetamide (DMAc), dimethyl sulfoxide
(DMSO), tetrahydrofuran (THF) or above-mentioned any a variety of combination.
18. a kind of preparation method of ultra-thin composite membrane according to claim 6 or 7, which is characterized in that described first has
Solvent includes the hydro carbons such as alkane and other nonpolarity and weak polar solvent.
19. a kind of preparation method of ultra-thin composite membrane according to claim 7 or 14, which is characterized in that described second
Organic solvent includes isopropanol.
20. a kind of preparation method of ultra-thin composite membrane according to claim 7, which is characterized in that the third is organic
Solvent includes ethyl alcohol.
21. a kind of preparation method of ultra-thin composite membrane according to claim 7, which is characterized in that the crosslinking temperature
Range is bubble point temperature of the room temperature to cross-linking agent solution, and the crosslinking time is 5min~4h.
22. a kind of preparation method of ultra-thin composite membrane according to claim 7, which is characterized in that the activation temperature
Range is bubble point temperature of the room temperature to activating reagent, and the activation time is 5min~120min.
23. a kind of preparation method of ultra-thin composite membrane according to claim 12, which is characterized in that the fragrant ternary
The mass percent concentration range of acyl chlorides is 0.005%~1.0%.
24. a kind of preparation method of ultra-thin composite membrane according to claim 7, which is characterized in that the crosslinking agent
Mass percent concentration range is 1.0%~20.0%.
25. a kind of application of ultra-thin composite membrane, which is characterized in that be used for organic solvent system isolation and purification and water solution system
Isolation and purification, and aqueous simultaneously and organic solvent solution system solute and solvent isolation and purification, wherein solute
Molecular weight ranges be 200~1000 dalton；
Wherein, a kind of hybridization compounding film is a kind of hybridization compounding film described in claim 1-4 any one, Huo Zheyou
Hybridization compounding film made from preparation method described in claim 5~24 any one.
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