WO2018205823A1 - Membrane d'osmose inverse et son procédé de fabrication - Google Patents

Membrane d'osmose inverse et son procédé de fabrication Download PDF

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Publication number
WO2018205823A1
WO2018205823A1 PCT/CN2018/084074 CN2018084074W WO2018205823A1 WO 2018205823 A1 WO2018205823 A1 WO 2018205823A1 CN 2018084074 W CN2018084074 W CN 2018084074W WO 2018205823 A1 WO2018205823 A1 WO 2018205823A1
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WO
WIPO (PCT)
Prior art keywords
reverse osmosis
phase solution
osmosis membrane
membrane
porous support
Prior art date
Application number
PCT/CN2018/084074
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English (en)
Chinese (zh)
Inventor
赵慧宇
Original Assignee
江苏拓邦环保科技有限公司
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Publication of WO2018205823A1 publication Critical patent/WO2018205823A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/18—Pore-control agents or pore formers

Definitions

  • the present invention relates to a reverse osmosis membrane and a preparation method thereof, in particular to a fullerene derivative doped reverse osmosis membrane and a preparation method thereof, and belongs to the technical field of water treatment membrane separation, and the present application requires a prior application in China (application) No. 201710322649.9) priority.
  • the current reverse osmosis technology mostly uses a composite membrane.
  • the composite membrane is the fastest growing and most widely used membrane variety because it can optimize the membrane rejection, water flux, stability and other properties.
  • the % reverse osmosis membrane is a composite membrane.
  • Composite membrane refers to a combination of a thin, dense, and special separation function on a porous support base film. Compared with the integrated film, the thickness of the surface dense layer of the composite film is thinner, so that the film has high solute separation rate and water transmission rate at the same time, and an optimized physical and chemical structure can satisfy various selective separations. demand.
  • the composite membranes currently widely used in the water treatment industry mainly adopt interfacial polymerization to laminate the polyamide film to the surface of the microporous support base film.
  • the usual process such as Chinese patents CN1817433A, CN101462025A, CN105664742A and many other domestic patents are public.
  • reverse osmosis membrane As a kind of filter membrane, reverse osmosis membrane has been one of the concerns of its service life and water permeability.
  • the structure of many composite reverse osmosis membranes is due to Multi-layer, although the desalination performance is improved, the water flux is reduced due to the accumulation of dirt after long-term use, so that the reverse osmosis efficiency is lowered, and the doping of the hydrophilic material in the membrane material can improve the passage of the reverse osmosis membrane.
  • the amount of water as modified by hydrophilic groups.
  • more and more methods have been used to increase the water flow rate by adding a modifier to the reverse osmosis membrane, but this method also brings many additional problems, such as increased production cost, complicated process, and membrane stability. Poor and so on.
  • the fullerene has very good hydrophilic properties and macromolecular structure, and its doping into the reverse osmosis membrane unexpectedly enhances the water flux effect, but the fullerene structure is too stable, and The whole is spherical, resulting in poor binding performance of the molecular grade to the polymer film, and easy to fall off.
  • the derivative of the fullerene was doped into the polyurethane film, and not only the molecule thereof Incorporating into the film layer, it can also act as a porogen in the film layer, and the strong fullerene derivative at the bonding portion It can be detached under the action of ultrasonic waves, thereby leaving nano-spherical pores.
  • This kind of pores and the combination of better fullerene derivatives have an effect on the inner and outer layers of the film layer, strengthen the three-dimensional void structure of the film layer, and improve the film layer. Water permeable, there has been no report on the application of fullerene derivatives to polyurethane reverse osmosis membranes.
  • the present application is directed to solving the problem of low water flow rate of the reverse osmosis membrane in the prior art, to provide a composite reverse osmosis membrane capable of increasing the water flow rate and a preparation method thereof.
  • the purpose of the application is to provide a reverse osmosis membrane and a preparation method thereof, so as to improve the water flow rate and solve the defects that most of the current reverse osmosis membranes have low water flow.
  • the present application proposes a reverse osmosis membrane comprising a reverse osmosis membrane and a fullerene derivative dispersed in the reverse osmosis membrane.
  • the reverse osmosis membrane comprises a porous support layer and a polyamide functional layer
  • the fullerene derivative is dispersed in the polyamide layer
  • the polyamide functional layer has a nanospherical microporous structure left after the fullerene derivative is washed away.
  • the porous support layer is selected from the group consisting of a polysulfone porous support membrane, a polyethersulfone porous support membrane or a polyacrylonitrile porous support membrane, preferably a polysulfone porous support membrane.
  • the derivative of the fullerene is selected from a derivative of C60, C72 or C82, and preferably the fullerene derivative is PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester, [6 , 6]-Phenyl-C73-Butyric Acid Methyl Ester, [6,6]-Phenyl-C83-Butyric Acid Methyl Ester).
  • the present application also provides a method for preparing the above reverse osmosis membrane, comprising the following steps:
  • aqueous phase solution dissolving the aromatic amine in water to prepare an aqueous phase solution having a mass fraction of 0.1-5%, preferably a mass fraction of 1-2%;
  • Interfacial polymerization the porous support membrane is immersed in the aqueous phase solution, and the aqueous phase solution remaining on the surface of the porous support membrane is removed after removal, and the surface of the porous support membrane is contacted with the oil phase solution to carry out interfacial polymerization reaction for 30-80 s.
  • a reverse osmosis membrane is obtained, and the reverse osmosis membrane is taken out from the oil phase solution, and dried to obtain the reverse osmosis membrane.
  • the aromatic amine described in the step 1) is at least one of p-phenylenediamine, m-phenylenediamine and trimestriamine;
  • the aromatic acid chloride described in the step 2) is at least one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, diphenyl dichloride, and trimesoyl chloride;
  • step 1) is ultrapure water
  • the organic solvent in the step 2) is selected from the group consisting of n-hexane, petroleum ether, cyclohexane, isopar series solvent, methylcyclohexane, ethyl cyclohexane;
  • the reverse osmosis membrane is removed from the oil phase solution in the step 4), it is vacuum dried at 30 to 80 ° C for 5 to 30 minutes, and then placed in ultrapure water to remove the PCBM and then stored.
  • the ultrasonic cleaning temperature is 30 to 40 ° C
  • the time is 10 to 60 min
  • the ultrasonic frequency is 20 to 40 kHz.
  • fullerene derivatives are commercially available, such as those obtained from manufacturers such as BEHRINGER and Wuhan Zhuoxin.
  • the reverse osmosis membrane of the present application has been proved to have good water permeability through test application, and the fullerene derivative is doped in the polyamide functional film layer, and the fullerene derivative has strong hydrophilic property, and
  • the unique spherical structure enables the original single-plane polyamide film to form a rugged multi-dimensional structure, which facilitates the passage of water molecules.
  • the polyamide film layer there are some fullerene derivative molecules, which are cross-bonded with the polyamide molecular network through the hydrogen bond on the derivative branch, and the combination is relatively strong, and other fullerenes
  • the derivative molecules and the polyamide network structure fail to form hydrogen bonds, only the intermolecular forces or physical inclusions between the layers, the bonding is not strong, and for the weakly bound molecules of these fullerene derivatives, rich
  • the hydrophilicity of the molecules of the olefinic derivatives is washed away by high-energy ultrasonic waves. After the molecules of these fullerene derivatives are detached, a number of spheres resembling the molecular size of the graphene derivative are formed in the polyamide film layer.
  • the solid graphene of these joints can act as a porogen, and the spherical pores formed after detachment can further pass water molecules, strengthen the water flux of the reverse osmosis membrane layer, and thereby increase the life of the reverse osmosis membrane.
  • Interfacial polymerization the polysulfone porous support membrane is immersed in the aqueous phase solution, and after removing, the aqueous phase solution remaining on the surface of the porous support membrane is removed, and the surface of the porous support membrane is contacted with the oil phase solution to carry out interfacial polymerization reaction. 40s, get the reverse osmosis membrane, take the reverse osmosis membrane out of the oil phase solution, dry it in an oven at 60 ° C for 10 min, then remove it by ultrasonic cleaning in 30 ° C ultrapure water to remove PCBM15min, ultrasonic frequency 25kHz, get doped Reverse osmosis membrane of PCBM.
  • Interfacial polymerization the polysulfone porous support membrane is immersed in the aqueous phase solution, and after removing, the aqueous phase solution remaining on the surface of the porous support membrane is removed, and the surface of the porous support membrane is contacted with the oil phase solution to carry out interfacial polymerization reaction.
  • 45s get the reverse osmosis membrane, take the reverse osmosis membrane out of the oil phase solution, dry it in an oven at 60 ° C for 8 min, then place it in a 30 ° C ultrapure water for ultrasonic cleaning to remove PCBM 15 min, ultrasonic frequency 30 kHz, that is, doping Reverse osmosis membrane of PCBM.
  • Interfacial polymerization the polysulfone porous support membrane is immersed in the aqueous phase solution, and after removing, the aqueous phase solution remaining on the surface of the porous support membrane is removed, and the surface of the porous support membrane is contacted with the oil phase solution to carry out interfacial polymerization reaction. 45s, get the reverse osmosis membrane, take the reverse osmosis membrane out of the oil phase solution, dry in the oven at 60 ° C for 8 min, then remove it in the ultra-pure water of 35 ° C ultrasonic cleaning to remove PCBM15min, ultrasonic frequency 35kHz, get doped Reverse osmosis membrane of PCBM.
  • Interfacial polymerization the polysulfone porous support membrane is immersed in the aqueous phase solution, and after removing, the aqueous phase solution remaining on the surface of the porous support membrane is removed, and the surface of the porous support membrane is contacted with the oil phase solution to carry out interfacial polymerization reaction.
  • 50s get the reverse osmosis membrane, take the reverse osmosis membrane out of the oil phase solution, dry it in the oven at 80 ° C for 5 min, then remove it by ultrasonic cleaning in 40 ° C ultrapure water to remove PCBM for 10 min, the ultrasonic frequency is 40 kHz, then the doping is obtained.
  • Reverse osmosis membrane of PCBM Reverse osmosis membrane of PCBM.
  • Interfacial polymerization the polysulfone porous support membrane is immersed in the aqueous phase solution, and after removing, the aqueous phase solution remaining on the surface of the porous support membrane is removed, and the surface of the porous support membrane is contacted with the oil phase solution to carry out interfacial polymerization reaction. 40 s, a reverse osmosis membrane was obtained, and the reverse osmosis membrane was taken out from the oil phase solution and dried in an oven at 70 ° C for 8 min to obtain a reverse osmosis membrane without doping PCBM.
  • the composite reverse osmosis membranes prepared in Examples 1-3 and Comparative Examples were subjected to a reverse osmosis operation test to test the corresponding salt rejection ratio (REJ) and water flux.
  • REJ salt rejection ratio
  • Test initial conditions raw water salinity (NaCL) 1500PPM, operating pressure 150PSI
  • the salt rejection rate (R) is defined as the difference between the feed liquid salt concentration (c f ) and the permeate salt concentration (c p ) at a certain temperature and operating pressure, divided by the feed liquid salt concentration (cf). .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane d'osmose inverse et son procédé de préparation, la membrane d'osmose inverse comprenant une membrane d'osmose inverse et un dérivé de fullerène, de préférence PCBM en tant que dérivé de fullerène, dispersé dans la membrane d'osmose inverse. Le procédé de préparation consiste la préparation d'une solution de phase aqueuse, dans laquelle m-phénylènediamine est dissoute, et une solution de phase huileuse, dans laquelle du chlorure de trimesoyle est dissous; puis dissolution de PCBM dans la solution de phase huileuse; et soumission celle-ci à une polymérisation interfaciale pour obtenir une membrane d'osmose inverse. Par introduction de PCMB dans une couche de membrane de polyamide et retrait sélectif de celle-ci, une couche de membrane ayant une structure de pore nanosphérique est obtenue, et la perméabilité à l'eau de la membrane peut être améliorée.
PCT/CN2018/084074 2017-05-09 2018-04-23 Membrane d'osmose inverse et son procédé de fabrication WO2018205823A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710322649.9A CN107138060B (zh) 2017-05-09 2017-05-09 一种反渗透膜及其制备方法
CN201710322649.9 2017-05-09

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WO2018205823A1 true WO2018205823A1 (fr) 2018-11-15

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Publication number Priority date Publication date Assignee Title
CN107138060B (zh) * 2017-05-09 2018-06-29 江苏拓邦环保科技有限公司 一种反渗透膜及其制备方法
CN107737528A (zh) * 2017-11-08 2018-02-27 江苏拓邦环保科技有限公司 一种反渗透膜及其制备方法
CN109126486A (zh) * 2018-09-26 2019-01-04 青岛科技大学 一种本体掺杂cno改性的聚酰胺反渗透膜及其制备方法和应用

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