CN105080366A - Reverse osmosis membrane and preparation method thereof - Google Patents
Reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a reverse osmosis membrane and a preparation method thereof, and belongs to the technical field of membrane separation. The reverse osmosis membrane comprises metal fullerene dispersed in the reverse osmosis membrane, wherein the metal fullerene is preferably Gd@C82, ie., metal gadolinium embedding C82. The present invention further provides a preparation method of the reverse osmosis membrane, wherein the method comprises: preparing a water phase solution with m-phenylenediamine dissolved inside and an oil phase solution with trimesoyl chloride dissolved inside, dissolving fullerene in the oil phase solution or dissolving hydroxylated fullerene in the water phase solution, and carrying out interfacial polymerization to obtain the reverse osmosis membrane. According to the present invention, the a unique cage-like structure, the nanometer pore structure and the good water molecule mass transfer channel effect of the metal fullerene are utilized to introduce the metal fullerene into the polyamide separation layer, such that the water flux and the salt rejection rate of the reverse osmosis membrane can be effectively improved, and the reverse osmosis membrane has good antibacterial property.
Description
Technical field
The present invention relates to a kind of reverse osmosis membrane and preparation method thereof, be specifically related to a kind of polyamide reverse osmosis composite film containing embedded metal fullerene and preparation method thereof, belong to technical field of membrane separation.
Background technology
Counter-infiltration is called as " water-purifying technique of 21 century ", has that purifying rate is high, low cost and other advantages, is widely used in the field such as bitter and desalinization, ultra-pure water preparation and Industrial Waste Water Treatments.The core of reverse osmosis technology is the Study and Development of high-performance reverse osmosis composite membrane, and current commercial reverse osmosis composite membrane is prepared by interfacial polymerization process mostly.Because polyamide contains the amide group (-CONH-) of good hydrophilic property, and having good mechanical stability, heat endurance and hydrolytic stability, is most typical reverse osmosis membrane materials.In recent years, the performance improving film by introducing the inorganic nano material that water can be promoted to transmit in reverse osmosis membrane aromatic polyamides Motor cortex becomes the study hotspot in reverse osmosis membrane field, and the inorganic nano material related to comprises nano metal, nano silicon, nano zeolite, imvite, CNT and various functionalized carbon nano-tube, Graphene and derivative thereof.Nano material-the composite membrane of polymer formed thus has following characteristics: one is the section pore structure that nano material effectively can improve polymer, thus improves composite membrane permeance property and separative efficiency; Two is that nano material can effectively improve polymer film surface physicochemical characteristic and microscopic appearance, reduces the interface behavior on pollutant and film surface in water body, alleviates fouling membrane.
Be all the fullerene of carbon nanomaterial, its structure is the convex polyhedron with pentagon and hexagonal surfaces composition.Because fullerene itself is a kind of very strong electron acceptor, its cage structure is carried out functional modification will obtain having the new function material of excellent properties.Wherein, TXEndohedral Metallofullerenes makes it have the physical and chemical performance different with fullerene because there is electron transfer between embedded metallic atom from Fullerene Carbon cage, there is some characteristic of fullerene and metal simultaneously, as stable, specific area are polyfunctionalized greatly, easily, and the good biologically active such as antibacterial, antiviral.The greatest problem that reverse osmosis separating membrane exists is fouling membrane, and the fouling membrane that especially microorganism causes can make membrane separating property decline, thus shortening film service life.Therefore, if introduce in reverse osmosis membrane by nano fullerene, membrane pollution problem will be solved.
But fullerene is hydrophobic substance, and in most of solvent, dissolubility is very poor.It is found that, if carry out chemical modification to fullerene, the dissolubility of the fullerene derivate obtained obviously strengthens.For embedded metal fullerene, due to the interaction of metallic element and fullerene, its dissolubility in organic solvent obviously can be improved.Up to the present, have been found that the 3rd B metal element (comprising Sc, Y and lanthanide series metal) can inclusion at some larger fullerenes as C
80, C
82and C
84in.At present, the most successful separation method is high performance liquid chromatography (HPLC), utilizes this method, be successfully separated, the some fullerenes metals of purifying, as ScC
84, YC
82, LaC
82, GdC
82, La
2c
80, Sc
2c
84and Sc
3c
82deng.But because the carbon basket structure of fullerene has strong lipophilicity, the solubility in polar solvent (as water) is very limited, greatly limit its investigation and application in living things system, also fullerene is not introduced the report of reverse osmosis membrane at present.
Summary of the invention
An object of the present invention is to provide a kind of reverse osmosis membrane, and described reverse osmosis membrane contains metal fullerene, has high flux, high salt-stopping rate and good anti-microbial property, can be applicable to water treatment field.
Another object of the present invention is to provide the preparation method of described reverse osmosis membrane, by by after metal fullerene functionalization again with polyamide functional layer compound, solving in prior art fullerene can not directly and the problem of the effective compound of reverse osmosis membrane.
For achieving the above object, the invention provides a kind of reverse osmosis membrane, it comprises reverse osmosis membrane and is dispersed in the metal fullerene in described reverse osmosis membrane.
The implication of described metal fullerene is the fullerene of embedded metal, and preferred described metal is the 3rd B metal element, comprises Sc, Y and lanthanide series metal, and described fullerene is selected from C
80, C
82or C
84, more preferably described metal fullerene is GdC
82, i.e. the C of embedded metal gadolinium
82.
In the present context, term " fullerene " means the various molecules comprising the hollow structure form be made up of carbon completely, such as spherical, ellipsoid, tubulose etc.Described structure must make them can catch at least one metallic atom, and therefore described structure must comprise the cavity that at least one is closed, and this cavity provides the sufficient space be captured in by least one metallic atom wherein.
Present invention also offers the preparation method of described reverse osmosis membrane, comprising:
1) preparation of aqueous phase solution: be dissolved in water by m-phenylene diamine (MPD) (MPD), is mixed with the aqueous phase solution that mass fraction is 0.5-3%.
2) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride (TMC) is dissolved in organic solvent, is mixed with the oil-phase solution that mass fraction is 0.05-0.2%.
3) metal fullerene is dissolved in described oil-phase solution, or be dissolved in by hydroxylated metal fullerene in described aqueous phase solution, the mass fraction of described metal fullerene in oil-phase solution or the mass fraction of described hydroxylated metal fullerene in aqueous phase solution are 0.01-0.2%.
4) interfacial polymerization: porous support membrane is immersed in aqueous phase solution, the aqueous phase solution that after taking out, removing porous support membrane surface is remaining, again interface polymerization reaction is carried out with oil-phase solution single-contact in described porous support membrane surface, obtain nascent state hydridization reverse osmosis membrane, described nascent state hydridization reverse osmosis membrane is taken out from oil-phase solution, after drying, obtains reverse osmosis membrane of the present invention.
Wherein, preferred steps 1) in water be ultra-pure water, the conducting medium namely in water is almost removed completely, and the colloidal substance of dissociation, gas and organic matter all do not remove the water to very low degree, at its 25 DEG C, resistivity is greater than 18M Ω cm, or close to the limiting value of 18.3M Ω cm.
Preferred steps 2) in organic solvent be selected from least one in n-hexane, dodecane and the tetradecane.Although dissolve fullerene usually use aromatic solvent (as toluene, chlorobenzene), it also has certain solubility in alkane solvents, but the organic solvent of filter membrane system is generally nontoxic, do not advise using virose aromatic solvent, therefore preferably adopt alkane as solvent.
Preferred steps 3) in metal fullerene be GdC
82, hydroxylated metal fullerene is hydroxylated GdC
82.Described hydroxylated metal fullerene implication be outside fullerene molecule structure on there is the derivative of the hydroxyl be covalently attached on it, the example is the fullerene with multiple hydroxyl.Hydroxylating is the functionalization to metal fullerene, and hydroxylated metal fullerene is water miscible, does not have hydroxylated metal fullerene to be only dissolved in organic solution.
Preferred steps 4) in porous support membrane be selected from polysulfone porous support membrane, polyurethane cellular support membrane or polypropylene porous support membrane.Polysulfones is easy to get due to its raw material, and masking is simple, has good mechanical strength and the close property of resistance to compression, and can antibiont degraded, so further preferred described porous support membrane is polysulfone porous support membrane.Described porous support membrane main body is non-woven fabrics, the polymer such as polysulfones are scribbled at the one side of non-woven fabrics, that the one side scribbling polymer contacts with oil-phase solution when carrying out interface polymerization reaction, on one side, aqueous solutes m-phenylene diamine (MPD) and oil phase solute pyromellitic trimethylsilyl chloride react and generate polyamide, and the reverse osmosis membrane obtained also is called polyamide reverse osmose membrane.
Preferred steps 4) described in nascent state hydridization reverse osmosis membrane take out from oil-phase solution, at 50 ~ 120 DEG C dry 5 ~ 10 minutes, be then placed in ultra-pure water and preserve.
In one particular embodiment of the present invention, described GdC
82prepared by arc process, purity >99.9%.
In one embodiment of the invention, GdC
82hydroxylacion method comprise: by GdC
82toluene solution and NaOH aqueous solution, with TBAH (TBAH) for catalyst, stirred at ambient temperature obtains brown precipitate, precipitate water-soluble rear cross post be separated, obtain hydroxylated GdC
82.
In one particular embodiment of the present invention, GdC
82hydroxylacion method step be: be the GdC of 0.05mg/ml by concentration
82toluene solution and mass fraction be 50% NaOH aqueous solution, GdC
82toluene solution and the volume ratio of the NaOH aqueous solution be 10:1, add a small amount of mass fraction be the TBAH (TBAH) of 10% as catalyst, stirring reaction 2-3h removes toluene layer, and water layer evaporation is obtained brown precipitate.Be separated by sephadex-25 chromatographic column after precipitation is water-soluble, obtain hydroxylated GdC
82.
At present, in order to make nano material more effectively with reverse osmosis membrane separation layer compound, need to carry out hydrophilic organic process to nano material.For the fullerene of hydrophobic, can be dissolved in oily solution as the raw material preparing reverse osmosis membrane, also can by improve after its hydroxylating process water-soluble again with reverse osmosis membrane compound, so both improve water flux and the salt-stopping rate of reverse osmosis membrane, can ensure that again described reverse osmosis membrane has good antibiotic property, this possesses high water flux, salt rejection rate and high antibiotic property aspect for diffusion barrier is simultaneously a great improvement.
The invention has the beneficial effects as follows: utilize the cage structure of metal fullerene uniqueness, nano-pore structure and good hydrone mass transfer channel effect, be introduced in polyamide separating layer by interface polymerization reaction, effectively can improve water flux and the salt-stopping rate of reverse osmosis membrane, and make described reverse osmosis membrane have good anti-microbial property.
Detailed description of the invention
Embodiment given below is in order to the present invention is described, instead of limits the invention.
Embodiment and comparative example are the preparation of reverse osmosis membrane, and wherein embodiment 1 adds GdC in oil-phase solution
82, embodiment 2 adds hydroxylated GdC in aqueous phase solution
82, comparative example 1 for add C in oil-phase solution
60, comparative example 2 for add C in aqueous phase solution
60aqueous suspensions.
C in embodiment 1 and 2
82prepared by arc process, concrete steps are: by high purity graphite (purity >99.9%) and Gd
2o
3fully mix with the mol ratio of 1:25, add adhesive phenolic resins press mold shaping, sinter in the high temperature furnace of 1600 DEG C, graphite rod after burned discharges the soot of synthesizing black on direct current electric arc device, after dimethyl formamide (DMF) solvent extraction, isolate GdC through HPLC
82, its purity >99.9%.
GdC in embodiment 2
82hydroxylated concrete steps are: be the GdC of 0.05mg/ml by concentration
82toluene solution and mass fraction be that the NaOH aqueous solution of 50% is with 10:1 volume mixture, add that volume is mixed solution 5%, mass fraction is that the TBAH (TBAH) of 10% is as catalyst, stirring reaction 2h removes colourless toluene layer, and water layer toluene cleans 3 times to remove unreacted GdC
82, then water layer evaporation is obtained brown precipitate, precipitate water-soluble after be separated by sephadex-25 chromatographic column, obtain yellow hydroxylating GdC
82.MALDI-TOF mass spectrum shows the GdC prepared
82and GdC
82(OH)
22for purer material, infrared spectrum (IR) and x-ray photoelectron power spectrum (XPS) show that the chemical formula of hydroxylated metal fullerene is GdC
82(OH)
22.
C in comparative example 1 and 2
60purchased from Suzhou great virtue carbon nanosecond science and technology Co., Ltd, purity 99.9%.
Embodiment 1
A. the preparation of aqueous phase solution: m-phenylene diamine (MPD) is dissolved and is dispersed in ultra-pure water, be mixed with the aqueous phase solution that mass fraction is 2%.
B. the preparation of oil-phase solution: pyromellitic trimethylsilyl chloride is dissolved and is dispersed in dodecane, be mixed with the oil-phase solution that mass fraction is 0.1%.
C. by GdC
82be dissolved in oil-phase solution, ultrasonic disperse makes it even, and mass fraction is 0.02%.
D. interfacial polymerization: polysulfones support membrane is immersed in the above-mentioned aqueous phase solution prepared, the aqueous phase solution that after taking out, removing is remaining, again interface polymerization reaction is carried out with oil-phase solution single-contact in this support membrane surface, put 70 DEG C of dryings in an oven after the nascent state hydridization reverse osmosis membrane taking-up of gained to take out for 5 minutes, be then placed in ultra-pure water and preserve.
Embodiment 2
A. the preparation of aqueous phase solution: m-phenylene diamine (MPD) is dissolved and is dispersed in ultra-pure water, be mixed with the aqueous phase solution that mass fraction is 2%.
B. the preparation of oil-phase solution: pyromellitic trimethylsilyl chloride is dissolved and is dispersed in organic solvent dodecane, be mixed with the oil-phase solution that mass fraction is 0.1%.
C. by GdC
82(OH)
22be dissolved in aqueous phase solution, ultrasonic disperse makes it even, and mass fraction is 0.02%.
D. interfacial polymerization: polysulfones support membrane is immersed in the above-mentioned aqueous solution prepared, the aqueous phase solution that after taking out, removing is remaining, again interface polymerization reaction is carried out with oil-phase solution single-contact in this support membrane surface, put 70 DEG C of dryings in an oven after the nascent state hydridization reverse osmosis membrane taking-up of gained to take out for 5 minutes, be then placed in ultra-pure water and preserve.
Comparative example 1
A. the preparation of aqueous phase solution: m-phenylene diamine (MPD) is dissolved and is dispersed in ultra-pure water, be mixed with the aqueous phase solution that mass fraction is 2%.
B. the preparation of oil-phase solution: pyromellitic trimethylsilyl chloride is dissolved and is dispersed in organic solvent dodecane, be mixed with the oil-phase solution that mass fraction is 0.1%.
C. by C
60be dissolved in oil-phase solution, ultrasonic disperse makes it even, and mass fraction is 0.02%.
D. interfacial polymerization: polysulfones support membrane is immersed in the above-mentioned aqueous solution prepared, the aqueous phase solution that after taking out, removing is remaining, again interface polymerization reaction is carried out with oil-phase solution single-contact in this support membrane surface, put 70 DEG C of dryings in an oven after the nascent state hydridization reverse osmosis membrane taking-up of gained to take out for 5 minutes, be then placed in ultra-pure water and preserve.
Comparative example 2
A. the preparation of aqueous phase solution: m-phenylene diamine (MPD) is dissolved and is dispersed in ultra-pure water, be mixed with the aqueous phase solution that mass fraction is 2%.
B. the preparation of oil-phase solution: pyromellitic trimethylsilyl chloride is dissolved and is dispersed in organic solvent dodecane, be mixed with the oil-phase solution that mass fraction is 0.1%.
C. first by fullerene C
60be dissolved in toluene and form saturated solution, then by saturated solution and distilled water with 1:10 volume mixture, two-phase separately after carry out again ultrasonic, when toluene volatilizees completely mutually, aqueous phase becomes yellow, illustrates that fullerene water suspension (Fullerenewatersuspensions, FWS) is formed.By C
60fWS is dissolved in aqueous phase solution, and ultrasonic disperse makes it even, and mass fraction is 0.02%.
D. interfacial polymerization: polysulfones support membrane is immersed in the above-mentioned aqueous solution prepared, the aqueous phase solution that after taking out, removing is remaining, again interface polymerization reaction is carried out with oil-phase solution single-contact in this support membrane surface, put 70 DEG C of dryings in an oven after the nascent state hydridization reverse osmosis membrane taking-up of gained to take out for 5 minutes, be then placed in ultra-pure water and preserve.
The test result of embodiment and comparative example is as shown in table 1.
Table 1
Wherein, water flux (F, L/m
2h) be defined as at certain temperature and operating pressure, through the water volume (V) of per membrane area (S) in the unit interval (t), computing formula is: F=V/ (St).
Salt rejection rate (R) is defined as at certain temperature and operating pressure, feeding liquid salinity (c
f) with permeate in salinity (c
p) difference, then divided by feeding liquid salinity (cf).Computing formula is: R (%)=(1-c
p/ c
f) × 100%.
The method of test membrane sterilizing rate is: employing Escherichia coli are experimental strain, the reverse osmosis membrane of embodiment and comparative example is cut into 10mm disk respectively, put into 4 100mL conical flasks crossed through autoclaving, add the Escherichia coli suspension of 20mL phosphate buffer solution and 100 μ L respectively, flask is fixed on shaking table and sways 20 hours with 150r/min, get afterwards 100 μ L sway after sample liquid carry out viable bacteria cultivate counting.Do contrast test with ordinary RO membrane simultaneously.The computing formula of sterilizing rate is: sterilizing rate=(A-B)/A × 100%, and wherein A is ordinary RO membrane sample viable count, and B is the reverse osmosis membrane sample viable count of embodiment or comparative example.Ordinary RO membrane is unadulterated polyamide reverse osmose membrane, and except not adding metal fullerene, all the other preparation process are with embodiment 1.
Desirable reverse osmosis membrane should have high water flux, high salt-stopping rate, anti-oxidant, acid and alkali-resistance, chlorine-resistant, antipollution and anti-microbial property.But high water flux and these two performance parameters of high salt-stopping rate are shifting trend, and reverse osmosis membrane will be made both to have had high flux and salt-stopping rate, there is again anti-microbial property and be also difficult to realize.In the prior art, usually can not sterilization when reverse osmosis membrane performance high (there is high flux and salt-stopping rate), can other performances of film of sterilization decline to some extent again.
Data as can be seen from table 1, embodiment 1 (adds GdC in oil-phase solution
82) and embodiment 2 (in aqueous phase solution, add hydroxylated GdC
82) water flux and salt-stopping rate all than the water flux (30.2L/m of ordinary RO membrane
2/ h) and salt-stopping rate (99.0%) increase, the performance of embodiment 2 improves more obvious.It should be noted that, in reverse osmosis membrane field, it is exactly very large progress that salt-stopping rate increases by 0.1%.Comprehensive, reverse osmosis membrane provided by the invention had both had high water flux and salt-stopping rate, had again good bactericidal property.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1. a reverse osmosis membrane, it comprises reverse osmosis membrane and is dispersed in the metal fullerene in described reverse osmosis membrane.
2. reverse osmosis membrane according to claim 1, is characterized in that, described metal is the 3rd B metal element, and described fullerene is selected from C
80, C
82or C
84, preferred described metal fullerene is GdC
82.
3. the preparation method of reverse osmosis membrane according to claim 1 and 2, is characterized in that, comprising:
1) preparation of aqueous phase solution: be dissolved in by m-phenylene diamine (MPD) in water, is mixed with the aqueous phase solution that mass fraction is 0.5-3%;
2) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride is dissolved in organic solvent, is mixed with the oil-phase solution that mass fraction is 0.05-0.2%;
3) metal fullerene is dissolved in described oil-phase solution, or be dissolved in by hydroxylated metal fullerene in described aqueous phase solution, the mass fraction of described metal fullerene in oil-phase solution or the mass fraction of described hydroxylated metal fullerene in aqueous phase solution are 0.01-0.2%;
4) interfacial polymerization: porous support membrane is immersed in aqueous phase solution, the aqueous phase solution that after taking out, removing porous support membrane surface is remaining, again interface polymerization reaction is carried out with oil-phase solution single-contact in described porous support membrane surface, obtain nascent state hydridization reverse osmosis membrane, described nascent state hydridization reverse osmosis membrane is taken out from oil-phase solution, after drying, obtains described reverse osmosis membrane.
4. method according to claim 3, is characterized in that, described step 1) in water be ultra-pure water.
5. method according to claim 3, is characterized in that, described step 2) in organic solvent be selected from least one in n-hexane, dodecane and the tetradecane.
6. method according to claim 3, is characterized in that, described step 3) in metal fullerene be GdC
82, hydroxylated metal fullerene is hydroxylated GdC
82.
7. method according to claim 3, is characterized in that, described step 4) in porous support membrane be selected from polysulfone porous support membrane, polyurethane cellular support membrane or polypropylene porous support membrane, be preferably polysulfone porous support membrane.
8. method according to claim 3, is characterized in that, described step 4) described in nascent state hydridization reverse osmosis membrane take out from oil-phase solution, at 50 ~ 120 DEG C dry 5 ~ 10 minutes, be then placed in ultra-pure water and preserve.
9. method according to claim 3, is characterized in that, described GdC
82prepared by arc process.
10. method according to claim 3, is characterized in that, described GdC
82hydroxylacion method comprise: by GdC
82toluene solution and NaOH aqueous solution, be catalyst with TBAH, stirred at ambient temperature is precipitated, will precipitate water-soluble rear cross post be separated, obtain hydroxylated GdC
82.
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| CN109224782A (en) * | 2018-09-29 | 2019-01-18 | 中国科学院大连化学物理研究所 | A kind of functionalized nano filler composite membrane and preparation method and application |
| CN111318171A (en) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | Processing and coating process of three-dimensional porous graphene filtering membrane |
| CN111686583A (en) * | 2019-03-13 | 2020-09-22 | 西陇科学股份有限公司 | Hydroxylated fullerene loaded nano-particle nanofiltration membrane and preparation method thereof |
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