CN105080366B - A kind of reverse osmosis membrane and preparation method thereof - Google Patents
A kind of reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of reverse osmosis membrane and preparation method thereof, belong to technical field of membrane separation.Metal fullerene in reverse osmosis membrane includes being dispersed in the reverse osmosis membrane, preferably described metal fullerene is Gd@C82, i.e. the C of embedded metal gadolinium82.Present invention also offers the preparation method of the reverse osmosis membrane, the aqueous phase solution of m-phenylene diamine (MPD) is dissolved with including preparation and be dissolved with the oil-phase solution of pyromellitic trimethylsilyl chloride, then metal fullerene is dissolved in the oil-phase solution, or hydroxylated metal fullerene is dissolved in the aqueous phase solution, the reverse osmosis membrane is obtained by interfacial polymerization.The present invention is using the unique cage structure of metal fullerene, nano-pore structure and good hydrone mass transfer channel effect, it is introduced into polyamide separating layer, the water flux and salt-stopping rate of reverse osmosis membrane can be effectively improved, and makes the reverse osmosis membrane that there is good anti-microbial property.
Description
Technical field
The present invention relates to a kind of reverse osmosis membrane and preparation method thereof, and in particular to a kind of poly- containing embedded metal fullerene
Acid amides reverse osmosis composite membrane and preparation method thereof, belongs to technical field of membrane separation.
Background technology
Counter-infiltration is referred to as " water-purifying technique of 21 century ", with 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 high-performance reverse osmosis
The development and exploitation of saturating composite membrane, current commercialization reverse osmosis composite membrane are prepared by interfacial polymerization process mostly.Because of polyamide
Amide group (- CONH-) containing good hydrophilic property, and with preferable mechanical stability, heat endurance and hydrolytic stability, be
Most typical reverse osmosis membrane materials.In recent years, water can be promoted to pass by the introducing in reverse osmosis membrane aromatic polyamides Motor cortex
Defeated inorganic nano material improves the study hotspot of the performance as reverse osmosis membrane field of film, and the inorganic nano material being related to includes
Nano metal, nano silicon, nano zeolite, montmorillonite, CNT and various functions carbon nano tube, Graphene and its
Derivative.Nano material-the composite membrane of polymer being consequently formed has the characteristics that：One to be that nano material can be effectively improved poly-
The section pore structure of compound, so as to improve composite membrane permeance property and separative efficiency；Two is that nano material can be effectively improved
Polymer film surface physicochemical characteristic and microscopic appearance, reduce pollutant and the interface behavior on film surface in water body, mitigate fouling membrane.
The fullerene of carbon nanomaterial is all, its structure is the convex polyhedron constituted with pentagon and hexagonal surfaces.Yin Fu
It is in itself a kind of very strong electron acceptor to strangle alkene, and functional modification is carried out in its cage structure will be obtained with excellent properties
New function material.Wherein, TXEndohedral Metallofullerenes are moved because there is electronics between embedded metallic atom and Fullerene Carbon cage
Move and cause it that there is the physical and chemical performance different from fullerene, while there are some characteristics of fullerene and metal, it is such as steady
Fixed, specific surface area is big, be easily polyfunctionalized, and the good bioactivity such as antibacterial, antiviral.Reverse osmosis separating membrane is present
Greatest problem be fouling membrane, the fouling membrane that especially microorganism causes can decline membrane separating property, so as to shorten film use
Life-span.Therefore, if nano fullerene is introduced into reverse osmosis membrane, it will solve membrane pollution problem.
But fullerene is hydrophobic substance, and dissolubility is very poor in most of solvent.If it has been found that entered to fullerene
Row chemical modification, the dissolubility of the fullerene derivate for obtaining is remarkably reinforced.For embedded metal fullerene, due to metallic element
With the interaction of fullerene, its dissolubility in organic solvent can be obviously improved.Up to the present, it has been found that the 3rd
B metal element (including Sc, Y and lanthanide series metal) can be included in some larger fullerenes such as C80、C82And C84In.Mesh
Before, most successful separation method is high performance liquid chromatography (HPLC), using this method, if having had successfully been isolated, having purified
Dry fullerenes metal, such as Sc@C84、Y@C82、La@C82、Gd@C82、La2@C80、Sc2@C84And Sc3@C82Deng.But due to
The carbon basket structure of fullerene has strong lipophilicity, and the solubility in polar solvent (such as water) is very limited, greatly limit it
Research and application in living things system, there is presently no the report that fullerene is introduced reverse osmosis membrane.
The content of the invention
An object of the present invention is to provide a kind of reverse osmosis membrane, and the reverse osmosis membrane contains metal fullerene, with height
Flux, salt-stopping rate high and good anti-microbial property, can be applied to water treatment field.
It is yet another object of the invention to provide the preparation method of the reverse osmosis membrane, after by metal fullerene functionalization
It is compound with polyamide functional layer again, solve the problems, such as that fullerene can not be directly effectively compound with reverse osmosis membrane in the prior art.
To achieve the above object, the invention provides a kind of reverse osmosis membrane, it includes reverse osmosis membrane and is dispersed in described anti-
Metal fullerene in permeable membrane.
The implication of the metal fullerene is the fullerene of embedded metal, and preferably described metal is the 3rd B metal unit
Element, including Sc, Y and lanthanide series metal, the fullerene are selected from C80、C82Or C84, more preferably described metal fullerene is Gd@C82, i.e.,
The C of embedded metal gadolinium82。
In the present context, term " fullerene " means to include various points of the hollow structure form being made up of carbon completely
Son, such as spherical, ellipsoid, tubulose etc..The structure must allow them to capture at least one metallic atom, therefore institute
Stating structure must be comprising the cavity of at least one closing, and the cavity provides the capturing wherein at least one metallic atom of abundance
Space.
Present invention also offers the preparation method of the reverse osmosis membrane, including：
1) preparation of aqueous phase solution：M-phenylene diamine (MPD) (MPD) is dissolved in water, it is 0.5-3%'s to be configured to mass fraction
Aqueous phase solution.
2) preparation of oil-phase solution：By pyromellitic trimethylsilyl chloride (TMC) dissolving in organic solvent, being configured to mass fraction is
The oil-phase solution of 0.05-0.2%.
3) metal fullerene is dissolved in the oil-phase solution, or hydroxylated metal fullerene is dissolved in described
In aqueous phase solution, mass fraction or the hydroxylated metal fullerene of the metal fullerene in oil-phase solution are in water phase
Mass fraction in solution is 0.01-0.2%.
4) interfacial polymerization：Porous support membrane is immersed in aqueous phase solution, porous support membrane surface remaining is removed after taking-up
Aqueous phase solution, then the porous support membrane surface and oil-phase solution single-contact are carried out into interface polymerization reaction, come into being
State hydridization reverse osmosis membrane, the nascent state hydridization reverse osmosis membrane is taken out from oil-phase solution, obtains of the present invention after drying
Reverse osmosis membrane.
Wherein, preferred steps 1) in water almost remove completely for the conducting medium in ultra-pure water, i.e. water, the glue not dissociated
Body material, gas and organic matter are removed to the water of very low degree, and resistivity is more than 18M Ω cm at its 25 DEG C, or close
The limiting value of 18.3M Ω cm.
Preferred steps 2) in organic solvent be selected from n-hexane, dodecane and the tetradecane at least one.Although dissolving
Usually using aromatic solvent (such as toluene, chlorobenzene), it also has certain solubility, but filter membrane to fullerene in alkane solvents
The organic solvent of system is usually nontoxic, it is not recommended that uses virose aromatic solvent, therefore makees preferably with alkane
It is solvent.
Preferred steps 3) in metal fullerene be Gd@C82, hydroxylated metal fullerene is hydroxylated Gd@C82.Institute
State hydroxylated metal fullerene implication be on the outside of fullerene molecule structure on have and be covalently attached to spreading out for hydroxyl thereon
Biology, the example is the fullerene with multiple hydroxyls.Hydroxylating is the functionalization to metal fullerene, hydroxylated gold
Category 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 it is many
Hole support membrane.Polysulfones is easy to get due to its raw material, and masking is simple, there is good mechanical strength and the close property of resistance to compression, and can antibiont drop
Solution, so further preferably the porous support membrane is polysulfone porous support membrane.The porous support membrane main body is non-woven fabrics,
The one side of non-woven fabrics scribbles the polymer such as polysulfones, carries out being to scribble the one side and oil-phase solution of polymer during interface polymerization reaction
Contact, aqueous solutes m-phenylene diamine (MPD) and oil phase solute pyromellitic trimethylsilyl chloride reaction generation polyamide, the reverse osmosis for obtaining on one side
Permeable membrane is also referred to as polyamide reverse osmose membrane.
Preferred steps 4) described in nascent state hydridization reverse osmosis membrane taken out from oil-phase solution, at 50~120 DEG C dry 5
~10 minutes, it is subsequently placed in preservation in ultra-pure water.
In one particular embodiment of the present invention, the Gd@C82Prepared by arc process, purity>99.9%.
In one embodiment of the invention, Gd@C82Hydroxylacion method include：By Gd@C82Toluene solution and NaOH
The aqueous solution mixes, and with TBAH (TBAH) as catalyst, stirring at room temperature obtains brown precipitate, precipitates water-soluble rear mistake
Post separation, obtains hydroxylated Gd@C82。
In one particular embodiment of the present invention, Gd@C82Hydroxylacion method step be：It is 0.05mg/ml by concentration
Gd@C82Toluene solution mix with the NaOH aqueous solution that mass fraction is 50%, Gd@C82Toluene solution it is water-soluble with NaOH
The volume ratio of liquid is 10:1, the TBAH (TBAH) that a small amount of mass fraction is 10% is added as catalyst, stirring
Reaction 2-3h removes toluene layer, and water layer evaporation is obtained into brown precipitate.To precipitate water-soluble rear by the chromatographic column of sephadex -25
Separated, obtained hydroxylated Gd@C82。
At present, in order that nano material is more effectively compound with reverse osmosis membrane separation layer, it is necessary to carry out parent to nano material
Water organic-treating.For the fullerene of hydrophobic, can be dissolved in oily solution as the raw material for preparing reverse osmosis membrane,
Can also be combined water solubility is improved after the treatment of its hydroxylating with reverse osmosis membrane again, so both improve the water flux of reverse osmosis membrane
And salt-stopping rate, can guarantee that the reverse osmosis membrane has good antibiotic property again, this is provided simultaneously with water flux high, takes off for seperation film
Salt rate and antibiotic property high aspect are a great improvement.
The beneficial effects of the invention are as follows：Using the unique cage structure of metal fullerene, nano-pore structure and good water
Molecular mass-transfer channeling, is introduced into polyamide separating layer by interface polymerization reaction, can effectively improve reverse osmosis membrane
Water flux and salt-stopping rate, and make the reverse osmosis membrane that there is good anti-microbial property.
Specific embodiment
Example given below is in order to illustrate the present invention, rather than limiting the invention.
Embodiment and comparative example are the preparation of reverse osmosis membrane, and wherein embodiment 1 adds Gd@C in oil-phase solution82, implement
Example 2 adds hydroxylated Gd@C in aqueous phase solution82, comparative example 1 is that C is added in oil-phase solution60, comparative example 2 is in water phase
C is added in solution60Aqueous suspensions.
C in embodiment 1 and 282Prepared by arc process, concretely comprised the following steps：By high purity graphite (purity>99.9%) with
Gd2O3With 1:25 mol ratio is sufficiently mixed, and adds the shaping of adhesive phenolic resin press mold, is carried out in 1600 DEG C of high temperature furnace
Sintering, it is burned after graphite rod discharged on direct current electric arc device the soot of synthesizing black, with dimethylformamide (DMF) solvent
After extraction, Gd@C are isolated by HPLC82, its purity>99.9%.
Gd@C in embodiment 282It is hydroxylated to concretely comprise the following steps：It is the Gd@C of 0.05mg/ml by concentration82Toluene it is molten
Liquid is with the NaOH aqueous solution that mass fraction is 50% with 10:1 volume mixture, it is the 5% of mixed solution, mass fraction to add volume
Be 10% TBAH (TBAH) as catalyst, stirring reaction 2h removes colourless toluene layer, water layer toluene
3 times are cleaned to remove unreacted Gd@C82, water layer evaporation is then obtained into brown precipitate, it is solidifying by glucan after precipitation is water-soluble
The chromatographic column of glue -25 is separated, and obtains the hydroxylating Gd@C of yellow82.MALDI-TOF mass spectrums show the Gd@C for preparing82And
Gd@C82(OH)22It is relatively purer material, infrared spectrum (IR) and x-ray photoelectron power spectrum (XPS) show hydroxylated gold
The chemical formula for belonging to fullerene is Gd@C82(OH)22。
C in comparative example 1 and 260Purchased 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) dissolving is dispersed in ultra-pure water, the water that mass fraction is 2% is configured to
Phase solution.
B. the preparation of oil-phase solution：Pyromellitic trimethylsilyl chloride dissolving is dispersed in dodecane, being configured to mass fraction is
0.1% oil-phase solution.
C. by Gd@C82It is dissolved in oil-phase solution, ultrasonic disperse is allowed to uniform, mass fraction is 0.02%.
D. interfacial polymerization：Polysulfones support membrane is immersed in the above-mentioned aqueous phase solution for preparing, the water of remaining is removed after taking-up
Phase solution, then the support membrane surface and oil-phase solution single-contact are carried out into interface polymerization reaction, the nascent state hydridization of gained is anti-
Permeable membrane is put 70 DEG C of dryings in an oven and is taken out for 5 minutes after taking out, be then placed on preservation in ultra-pure water.
Embodiment 2
A. the preparation of aqueous phase solution：M-phenylene diamine (MPD) dissolving is dispersed in ultra-pure water, the water that mass fraction is 2% is configured to
Phase solution.
B. the preparation of oil-phase solution：Pyromellitic trimethylsilyl chloride dissolving is dispersed in organic solvent dodecane, quality is configured to
Fraction is 0.1% oil-phase solution.
C. by Gd@C82(OH)22It is dissolved in aqueous phase solution, ultrasonic disperse is allowed to uniform, mass fraction is 0.02%.
D. interfacial polymerization：Polysulfones support membrane is immersed in the above-mentioned aqueous solution for preparing, the water phase of remaining is removed after taking-up
Solution, then the support membrane surface and oil-phase solution single-contact are carried out into interface polymerization reaction, the nascent state hydridization reverse osmosis of gained
Permeable membrane puts 70 DEG C of dryings taking-up in 5 minutes in an oven after taking out, be then placed on preservation in ultra-pure water.
Comparative example 1
A. the preparation of aqueous phase solution：M-phenylene diamine (MPD) dissolving is dispersed in ultra-pure water, the water that mass fraction is 2% is configured to
Phase solution.
B. the preparation of oil-phase solution：Pyromellitic trimethylsilyl chloride dissolving is dispersed in organic solvent dodecane, quality is configured to
Fraction is 0.1% oil-phase solution.
C. by C60It is dissolved in oil-phase solution, ultrasonic disperse is allowed to uniform, mass fraction is 0.02%.
D. interfacial polymerization：Polysulfones support membrane is immersed in the above-mentioned aqueous solution for preparing, the water phase of remaining is removed after taking-up
Solution, then the support membrane surface and oil-phase solution single-contact are carried out into interface polymerization reaction, the nascent state hydridization reverse osmosis of gained
Permeable membrane puts 70 DEG C of dryings taking-up in 5 minutes in an oven after taking out, be then placed on preservation in ultra-pure water.
Comparative example 2
A. the preparation of aqueous phase solution：M-phenylene diamine (MPD) dissolving is dispersed in ultra-pure water, the water that mass fraction is 2% is configured to
Phase solution.
B. the preparation of oil-phase solution：Pyromellitic trimethylsilyl chloride dissolving is dispersed in organic solvent dodecane, quality is configured to
Fraction is 0.1% oil-phase solution.
C. first by fullerene C60It is dissolved in toluene and forms saturated solution, then by saturated solution and distilled water with 1:10 volumes
Mixing, two-phase carries out ultrasound again after separating, and after toluene mutually volatilizees completely, water mutually turns into yellow, illustrates fullerene water suspension
(Fullerene water suspensions, FWS) has been formed.By C60FWS is dissolved in aqueous phase solution, and ultrasonic disperse is allowed to
Uniformly, mass fraction is 0.02%.
D. interfacial polymerization：Polysulfones support membrane is immersed in the above-mentioned aqueous solution for preparing, the water phase of remaining is removed after taking-up
Solution, then the support membrane surface and oil-phase solution single-contact are carried out into interface polymerization reaction, the nascent state hydridization reverse osmosis of gained
Permeable membrane puts 70 DEG C of dryings taking-up in 5 minutes in an oven after taking out, be then placed on preservation in ultra-pure water.
The test result of embodiment and comparative example is as shown in table 1.
Table 1
Wherein, water flux (F, L/m2H) it is defined as at certain temperature and operating pressure, in the unit interval (t) thoroughly
The water volume (V) of per membrane area (S) is crossed, computing formula is：F=V/ (St).
Salt rejection rate (R) is defined as at certain temperature and operating pressure, feeding liquid salinity (cf) with permeate in salt
Concentration (cp) difference, then divided by feeding liquid salinity (cf).Computing formula is：R (%)=(1-cp/cf) × 100%.
The method of test film sterilizing rate is：It is experimental strain to use Escherichia coli, by the counter-infiltration of embodiment and comparative example
Film is cut into 10mm disks respectively, is put into 4 100mL conical flasks crossed through autoclaving, is separately added into 20mL phosphoric acid buffers
The escherichia coli suspension of solution and 100 μ L, flask is fixed on shaking table and is swayed 20 hours with 150r/min, and 100 μ L are taken afterwards
Sample liquid after swaying carries out viable bacteria culture and counts.Contrast test is done with ordinary RO membrane simultaneously.The computing formula of sterilizing rate is：
Sterilizing rate=(A-B)/A × 100%, wherein A is ordinary RO membrane sample viable count, and B is the reverse osmosis of embodiment or comparative example
Permeable membrane sample viable count.Ordinary RO membrane is the polyamide reverse osmose membrane of undoped p, in addition to not adding metal fullerene, its
Remaining preparation process is with embodiment 1.
Preferable reverse osmosis membrane should have water flux high, salt-stopping rate high, anti-oxidant, acid and alkali-resistance, chlorine-resistant, antipollution and antibacterial
Performance.But water flux high and the two performance parameters of salt-stopping rate high will be such that reverse osmosis membrane both had in shifting trend
There are high flux and salt-stopping rate, and be also difficult to anti-microbial property.In the prior art, (have when reverse osmosis membrane performance is high
High flux and salt-stopping rate) when generally can not be sterilized, other performances of film that can be sterilized have declined again.
Data can be seen that embodiment 1 and (Gd@C be added in oil-phase solution from table 182) and embodiment 2 (mixed in water
Hydroxylated Gd@C are added in liquid82) water flux and salt-stopping rate all than the water flux (30.2L/m of ordinary RO membrane2/ h) and
Salt-stopping rate (99.0%) increases, and the performance of embodiment 2 improves more obvious.It should be noted that in reverse osmosis membrane field,
It is exactly very big progress that salt-stopping rate increases by 0.1%.For synthesis, the reverse osmosis membrane that the present invention is provided both had had water flux high and had cut
Salt rate, and with good bactericidal property.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (8)
1. a kind of preparation method of reverse osmosis membrane, the reverse osmosis membrane includes reverse osmosis membrane and is dispersed in the reverse osmosis membrane
Metal fullerene；
The preparation method of reverse osmosis membrane, including：
1) preparation of aqueous phase solution：M-phenylene diamine (MPD) is dissolved in water, the aqueous phase solution that mass fraction is 0.5-3% is configured to；
2) preparation of oil-phase solution：By pyromellitic trimethylsilyl chloride dissolving in organic solvent, mass fraction is configured to for 0.05-
0.2% oil-phase solution；
3) metal fullerene is dissolved in the oil-phase solution, or hydroxylated metal fullerene is dissolved in the water phase
In solution, mass fraction or the hydroxylated metal fullerene of the metal fullerene in oil-phase solution are in aqueous phase solution
In mass fraction be 0.01-0.2%；
4) interfacial polymerization：Porous support membrane is immersed in aqueous phase solution, the water of porous support membrane surface remaining is removed after taking-up
Phase solution, then the porous support membrane surface and oil-phase solution single-contact are carried out into interface polymerization reaction, obtain nascent state miscellaneous
Change reverse osmosis membrane, the nascent state hydridization reverse osmosis membrane is taken out from oil-phase solution, the reverse osmosis membrane is obtained after drying；
The step 3) in metal fullerene be Gd@C82, hydroxylated metal fullerene is hydroxylated Gd@C82。
2. method according to claim 1, it is characterised in that the step 1) in water be ultra-pure water.
3. method according to claim 1, it is characterised in that the step 2) in organic solvent be selected from n-hexane, ten
At least one in dioxane and the tetradecane.
4. method according to claim 1, it is characterised in that the step 4) in porous support membrane be selected from polysulfone porous
Support membrane, polyurethane cellular support membrane or polypropylene porous support membrane.
5. method according to claim 4, it is characterised in that the step 4) in porous support membrane be polysulfone porous branch
Support film.
6. method according to claim 1, it is characterised in that the step 4) described in nascent state hydridization reverse osmosis membrane from
Taken out in oil-phase solution, dried 5~10 minutes at 50~120 DEG C, be subsequently placed in preservation in ultra-pure water.
7. method according to claim 1, it is characterised in that the Gd@C82Prepared by arc process.
8. method according to claim 1, it is characterised in that the Gd@C82Hydroxylacion method include：By Gd@C82's
Toluene solution mixes with the NaOH aqueous solution, and with TBAH as catalyst, stirring at room temperature is precipitated, and will precipitate water
Post separation is crossed after molten, hydroxylated Gd@C are obtained82。
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| CN106178996A (en) * | 2016-08-03 | 2016-12-07 | 中国科学院城市环境研究所 | A kind of super-hydrophobic nano particle polyamide nano complex reverse osmosis membrane and preparation method thereof |
| CN107138060B (en) * | 2017-05-09 | 2018-06-29 | 江苏拓邦环保科技有限公司 | A kind of reverse osmosis membrane and preparation method thereof |
| CN107737528A (en) * | 2017-11-08 | 2018-02-27 | 江苏拓邦环保科技有限公司 | A kind of reverse osmosis membrane and preparation method thereof |
| CN109224782B (en) * | 2018-09-29 | 2021-02-12 | 中国科学院大连化学物理研究所 | Functionalized nano filler composite membrane, preparation method and application |
| CN111318171B (en) * | 2018-12-17 | 2022-06-24 | 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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