CN111214965A - Reverse osmosis membrane and preparation method and application thereof - Google Patents

Reverse osmosis membrane and preparation method and application thereof Download PDF

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Publication number
CN111214965A
CN111214965A CN201811420891.0A CN201811420891A CN111214965A CN 111214965 A CN111214965 A CN 111214965A CN 201811420891 A CN201811420891 A CN 201811420891A CN 111214965 A CN111214965 A CN 111214965A
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membrane
reverse osmosis
solution
carbon nanotube
polyamide
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靳健
高守建
朱玉长
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
    • A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Abstract

The invention discloses a reverse osmosis membrane and a preparation method and application thereof. The reverse osmosis membrane is a stable composite membrane integrating a porous filter membrane, a carbon nanotube membrane and a polyamide membrane, wherein the porous filter membrane is used as a substrate loaded by the carbon nanotube membrane and provides good mechanical strength; the carbon nanotube film has uniformly distributed nano-size pore diameter and high porosity, and is used as a support for interfacial polymerization reaction, so that the uniform distribution of a monomer solution and the controllable release of a monomer are realized, and the ultrathin high-quality polyamide film is prepared; the polyamide membrane is used as a performance determining layer, has the characteristic of ultra-thinness, and ensures that the flux of the novel reverse osmosis membrane is far higher than that of the traditional reverse osmosis membrane while keeping high rejection rate. The reverse osmosis membrane provided by the invention has the advantages that the carbon nanotube membrane intermediate layer with uniformly distributed nano-size apertures and high porosity is introduced for the first time, and the breakthrough performance is improved.

Description

Reverse osmosis membrane and preparation method and application thereof
Technical Field
The invention relates to a reverse osmosis membrane with a stable structure of a porous filter membrane supporting layer, a carbon nanotube membrane intermediate layer and a polyamide membrane selective layer, and a preparation process and application thereof, belonging to the technical field of material preparation and membrane separation.
Background
The reverse osmosis membrane is used as the core of the reverse osmosis technology, has extremely huge application markets in the fields of seawater desalination, brackish water desalination, drinking water purification, industrial sewage treatment, hemodialysis and the like, and the demand of reverse osmosis membrane components and reverse osmosis equipment is increased year by year. At present, the amount of fresh water produced by reverse osmosis membranes globally reaches 2 x 107Ton. According to research data of a research institute of high-industrial-product membrane materials, the market scale of the reverse osmosis membrane in China in 2017 reaches 44 hundred million yuan, and in 2020, the market scale of the reverse osmosis membrane reaches 87 hundred million yuan. The huge demand of reverse osmosis membranes and reverse osmosis technology in various application fields puts higher requirements on the flux of the reverse osmosis membranes, and the reverse osmosis membranes with high flux and high rejection rate are always the key points of scientific research and market demands.
Conventional reverse osmosis membranes are typically thin film composite membranes, which are composed of an ultrafiltration membrane support layer and a polyamide membrane selection layer. The ultrafiltration membrane supporting layer provides high mechanical strength for the reverse osmosis membrane, and the polyamide membrane selection layer determines the separation performance of the reverse osmosis membrane; the polyamide membrane selection layer is prepared by an interfacial polymerization reaction of polyamine aqueous phase solution and polybasic acyl chloride organic phase solution on the surface of an ultrafiltration membrane. At present, most of ultrafiltration membrane support layers in reverse osmosis membranes are traditional polysulfone ultrafiltration membranes, polyether sulfone ultrafiltration membranes, sulfonated polyether sulfone ultrafiltration membranes and the like. The traditional ultrafiltration membrane has very low surface porosity and very uneven pore distribution, and in the process of preparing the polyamide membrane selection layer by taking the traditional ultrafiltration membrane as a supporting layer, the monomer solution distribution and the monomer release speed are difficult to be effectively regulated and controlled, so that the thickness and the quality of the prepared polyamide membrane are difficult to be accurately controlled, and the polyamide membrane selection layer with extremely thin membrane thickness and no defects is difficult to obtain. The thickness of the polyamide membrane selection layer in a reverse osmosis membrane is typically in the range of hundreds to hundreds of nanometers. The selective layer is the basic source of the mass transfer resistance of the reverse osmosis membrane, so the flux of the current reverse osmosis membrane is very low. In addition, the thickness and the mass transfer resistance of the reverse osmosis membrane using the traditional ultrafiltration membrane as a supporting layer are difficult to be effectively reduced by changing the interfacial polymerization reaction conditions, so that the flux of the reverse osmosis membrane is greatly improved. On the other hand, the surface porosity of the traditional ultrafiltration membrane is very low, so that the effective water channel area of the polyamide membrane supported by the traditional ultrafiltration membrane is still greatly damaged, and the flux of the reverse osmosis membrane is low. In recent ten years, in order to improve the flux of the reverse osmosis membrane, people continuously provide improvements on the composition and the preparation method of the existing reverse osmosis membrane, and a series of novel reverse osmosis membranes are developed:
CN101569836A discloses a high-flux composite reverse osmosis membrane and a preparation method thereof. In this patent, a water-soluble additive is added to the aqueous phase solution to reduce the solubility difference between the aqueous phase and the organic phase, increase the overlapping miscibility of the two phases, and enhance the diffusion migration ability of polyamine monomers to the organic phase and the reaction ability with polyacyl chloride, thereby increasing the interfacial polymerization reaction zone and the selected surface roughness of the prepared polyamide membrane, and preparing a reverse osmosis membrane with a larger effective area and a higher flux.
CN1817422A discloses a reverse osmosis membrane with special selective separability and a preparation method thereof. In the patent, m-phenylenediamine and 2, 4-diaminobenzene sulfonic acid in certain proportion are used as polyamine monomers in an aqueous phase solution, and m-phthaloyl chloride and trimesoyl chloride in certain proportion are used as polybasic acyl chloride monomers in an organic phase solution to prepare a polyamide membrane selection layer through interfacial polymerization.
CN101940883A discloses a reverse osmosis membrane containing a nano zeolite molecular sieve and a preparation method thereof. In the patent, a nano zeolite molecular sieve is dispersed in a polyamine aqueous phase solution or a polybasic acyl chloride organic phase solution, and the nano zeolite molecular sieve is compounded into a prepared polyamide membrane selection layer through an interfacial polymerization reaction.
CN102802772A discloses a reverse osmosis membrane containing vertically aligned carbon nanotubes and a preparation method thereof. In this patent, carbon nanotubes aligned are formed at the interface of an aqueous phase solution and an organic phase solution, the aligned carbon nanotubes are compounded into a prepared polyamide membrane selection layer through an interfacial polymerization reaction, and the polyamide/carbon nanotube composite is transferred and bonded to a support layer.
CN101791522A discloses a composite reverse osmosis membrane containing carbon nano-tubes and a preparation method thereof. In the preparation of the polyamide film selection layer, carbon nanotubes are mixed into a monomer solution thereof, and a polyamide film containing carbon nanotubes is prepared through interfacial polymerization. The pore structure in the carbon nano tube improves the flux of the reverse osmosis composite membrane.
From the existing research, the newly developed reverse osmosis membrane is mainly prepared by changing the components of polyamine and polyacyl chloride or adding a nano material additive, but is still limited to the traditional membrane structure of the traditional ultrafiltration membrane supporting layer/polyamide membrane selection layer, the membrane flux is only partially improved, and the great change is difficult to realize. After all, the traditional ultrafiltration membrane is still difficult to accurately control the interfacial polymerization reaction process because of low surface porosity and uneven surface pore distribution, and an ultrathin high-quality polyamide membrane selection layer cannot be obtained to reduce the mass transfer resistance, so that the fundamental improvement of the flux of the reverse osmosis membrane is realized. Therefore, the research on the novel reverse osmosis membrane supporting layer with high porosity and uniformly distributed holes realizes the change of the traditional structure of the reverse osmosis membrane, realizes the fine regulation and control of the interfacial polymerization reaction process, prepares the ultra-thin and high-quality polyamide membrane selection layer, and further obtains the novel reverse osmosis membrane with high flux and high rejection rate, thereby having great scientific research value and economic benefit. However, no relevant research report is reported at present for the novel reverse osmosis membrane.
Disclosure of Invention
The invention mainly aims to provide a reverse osmosis membrane, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a reverse osmosis membrane which comprises a porous filter membrane supporting layer, a carbon nanotube membrane middle layer and a polyamide membrane selection layer which are sequentially arranged.
The embodiment of the invention also provides a preparation method of the reverse osmosis membrane, which comprises the following steps:
(1) loading the dispersion liquid of the carbon nano tubes modified by the carbon nano tubes or the hydrophilic materials on the surface of the porous filter membrane to obtain a reticular carbon nano tube membrane formed by alternately stacking the carbon nano tubes or the carbon nano tubes modified by the hydrophilic materials;
(2) dissolving polyamine in water to prepare a water phase solution with the concentration of 0.01-10 g/L; dissolving polybasic acyl chloride in an organic solvent to prepare an organic phase solution with the concentration of 0.001-10 g/L;
(3) contacting the surface of the carbon nanotube film with the aqueous phase solution, and removing the aqueous phase solution remained on the surface of the carbon nanotube film after the aqueous phase solution completely wets the surface of the carbon nanotube film; then contacting the surface of the carbon nano tube membrane contacted with the aqueous phase solution with the organic phase solution, and carrying out interfacial polymerization reaction on polyamine and polybasic acyl chloride on the surface of the carbon nano tube membrane to generate a polyamide membrane;
(4) removing redundant polybasic acyl chloride on the surface of the obtained polyamide membrane to obtain the reverse osmosis membrane.
The embodiment of the invention also provides application of the reverse osmosis membrane in seawater desalination, brackish water desalination, drinking water purification, industrial sewage treatment or hemodialysis.
The embodiment of the invention also provides a membrane separation device, which comprises the reverse osmosis membrane.
Compared with the prior art, the invention has the beneficial effects that:
the reverse osmosis membrane provided by the embodiment of the invention is a stable composite membrane integrating a porous filter membrane, a carbon nanotube membrane and a polyamide membrane. The porous filter membrane is used as a substrate loaded by the carbon nanotube membrane, so that good mechanical strength is provided; the carbon nanotube film has uniformly distributed nano-size pore diameter and high porosity, and is used as a support for interfacial polymerization reaction, so that the uniform distribution of a monomer solution and the controllable release of a monomer are realized, and the preparation of an ultrathin high-quality polyamide film is realized in a breakthrough manner; the polyamide membrane is used as a performance determining layer, has the characteristic of ultra-thinness, and realizes the great improvement of membrane flux while keeping high rejection rate.
Different from the traditional reverse osmosis membrane which uses an ultrafiltration membrane with low porosity and uneven pore size distribution as a support layer for interfacial polymerization reaction to prepare a polyamide membrane selection layer, the reverse osmosis membrane provided by the invention firstly introduces a carbon nanotube membrane intermediate layer with excellent mechanical and chemical stability, uniformly distributed nano-size pore sizes, ultrahigh porosity and ultrahigh membrane flux, and replaces the traditional ultrafiltration membrane support layer with the carbon nanotube membrane intermediate layer and a porous filter membrane in a composite way, so that the interfacial polymerization reaction is more accurately controlled, the ultrathin thickness and high quality of the polyamide membrane selection layer are realized, the novel reverse osmosis membrane has the flux far higher than that of the traditional reverse osmosis membrane while the high rejection rate is maintained, and the novel reverse osmosis membrane has breakthrough performance improvement. The characteristics show that the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer can separate 2000ppm NaCl solution under the conditions of 25 ℃, 1.6MPa of pressure and 7 of pH value, and the water flux can reach 50-100Lm-2h-1The NaCl desalting rate reaches more than 97 percent.
Drawings
FIG. 1a is a schematic diagram of the overall structure of a reverse osmosis membrane in an exemplary embodiment of the invention.
FIG. 1b is a front view of a reverse osmosis membrane in an exemplary embodiment of the invention.
FIG. 2a is a side SEM image of the middle layer of a carbon nanotube film in a reverse osmosis membrane prepared in example 1 of the present invention.
FIG. 2b is a surface SEM image of the intermediate layer of carbon nanotube film in the reverse osmosis membrane prepared in example 1 of the present invention.
FIG. 3 is an AFM photograph of the surface of the intermediate layer of the carbon nanotube film in the reverse osmosis membrane prepared in example 1 of the present invention.
FIG. 4 is a surface SEM photograph of a selective layer of a polyamide membrane in a reverse osmosis membrane prepared in example 1 of the present invention.
FIG. 5 is an AFM photograph of the surface of the selective layer of the polyamide membrane in the reverse osmosis membrane prepared in example 1 of the present invention.
FIG. 6 is a SEM photograph of the surface of a selective layer of a polyamide membrane in a reverse osmosis membrane prepared in example 2 of the present invention.
FIG. 7 is an AFM photograph of the surface of a selective layer of a polyamide membrane in a reverse osmosis membrane prepared in example 2 of the present invention.
Detailed Description
Aiming at the defects of the prior art, the inventor of the invention provides the technical scheme of the invention through long-term research and massive practice. The technical solution, its implementation and principles, etc. will be further explained as follows. It is to be understood, however, that within the scope of the present invention, each of the above-described features of the present invention and each of the features described in detail below (examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
In one aspect of the present invention, a reverse osmosis membrane includes a porous filter membrane support layer, a carbon nanotube membrane intermediate layer, and a polyamide membrane selective layer, which are sequentially provided.
Referring to fig. 1 a-1 b, the reverse osmosis membrane of the present invention includes a porous filter membrane support layer 1, a carbon nanotube membrane intermediate layer 2, and a polyamide membrane selective layer 3, which are sequentially disposed.
In some embodiments, the porous filter membrane support layer comprises a porous filter membrane.
In some more preferred embodiments, the porous filtration membrane is selected from a microfiltration membrane or an ultrafiltration membrane.
In some more preferred embodiments, the pore size of the porous filter membrane is 2nm to 20 μm.
In some preferred embodiments, the material of the porous filter membrane is selected from any one of a polymer membrane, an inorganic membrane and an organic-inorganic hybrid membrane.
Preferably, the porous filter membrane is selected from any one of a polyethersulfone membrane, a cellulose ester membrane, a nylon membrane and a zirconia ceramic membrane with a pore size of 0.22 μm, 0.45 μm or 0.8 μm.
In some embodiments, the carbon nanotube film intermediate layer is a mesh-like film formed by interpenetrating stacking of a plurality of carbon nanotubes.
It has an effective pore size comparable to conventional ultrafiltration membranes and a porosity much higher than conventional ultrafiltration membranes.
In some preferred embodiments, the carbon nanotubes include any one or a combination of two or more of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled carbon nanotubes modified with a hydrophilic material, double-walled carbon nanotubes modified with a hydrophilic material, and multi-walled carbon nanotubes modified with a hydrophilic material.
In some more preferred embodiments, the carbon nanotube film intermediate layer has a thickness of 20nm to 50 μm and a pore size of 1nm to 100 nm.
Preferably, the thickness of the carbon nanotube film intermediate layer is 50nm to 200nm, and the pore diameter is 5nm to 50 nm. The carbon nanotube is selected from single-wall carbon nanotube modified by dopamine, polydopamine, tannic acid, polyethyleneimine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinylpyrrolidone and Trotion X-100.
In some embodiments, the polyamide film selection layer comprises a polyamide film prepared from a polyamine and a polyacyl chloride by an interfacial polymerization reaction.
The embodiment of the invention also provides a preparation method of the reverse osmosis membrane, which comprises the following steps:
(1) loading the dispersion liquid of the carbon nano tubes modified by the carbon nano tubes or the hydrophilic materials on the surface of the porous filter membrane to obtain a reticular carbon nano tube membrane formed by alternately stacking the carbon nano tubes or the carbon nano tubes modified by the hydrophilic materials;
(2) dissolving polyamine in water to prepare a water phase solution with the concentration of 0.01-10 g/L; dissolving polybasic acyl chloride in an organic solvent to prepare an organic phase solution with the concentration of 0.001-10 g/L;
(3) contacting the surface of the carbon nanotube film with the aqueous phase solution, and removing the aqueous phase solution remained on the surface of the carbon nanotube film after the aqueous phase solution completely wets the surface of the carbon nanotube film; then contacting the surface of the carbon nano tube membrane contacted with the aqueous phase solution with the organic phase solution, and carrying out interfacial polymerization reaction on polyamine and polybasic acyl chloride on the surface of the carbon nano tube membrane to generate a polyamide membrane;
(4) removing redundant polybasic acyl chloride on the surface of the obtained polyamide membrane to obtain the reverse osmosis membrane.
Wherein the porous filter membrane in the reverse osmosis membrane preparation method is at least selected from one of a microfiltration membrane or an ultrafiltration membrane, the aperture range is 2 nm-20 mu m, and the material of the porous filter membrane is at least selected from one of a polymer membrane, an inorganic membrane and an organic-inorganic hybrid membrane.
Preferably, the porous filter membrane is selected from any one of a polyethersulfone membrane, a cellulose ester membrane, a nylon membrane and a zirconia ceramic membrane with the pore diameter of 0.22 μm, 0.45 μm or 0.8 μm.
Wherein the carbon nanotubes are selected from at least one of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes or a combination of more than two of the single-walled carbon nanotubes, the double-walled carbon nanotubes and the multi-walled carbon nanotubes.
Preferably, the carbon nanotubes are single-walled carbon nanotubes.
In some embodiments, the carbon nanotube film surface is contacted with the aqueous solution in step (3) in a submerged or coated manner for more than 5 seconds; and contacting the surface of the carbon nanotube film contacted with the aqueous phase solution with the organic phase solution in a manner of immersing or coating for 5-600 seconds.
In some embodiments, step (4) specifically comprises: removing redundant polybasic acyl chloride on the surface of the polyamide membrane, carrying out heat treatment at 40-100 ℃ for 0-60 min, and then carrying out post-treatment to obtain the reverse osmosis membrane.
In some embodiments, the hydrophilic material comprises dopamine, polydopamine, tannic acid, polyethyleneimine, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, or Trotion X-100.
In some embodiments, the polyamine comprises any one or a combination of two or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, p-phenylenediamine, s-phenylenediamine, and 5-sulfom-phenylenediamine.
In some embodiments, the poly-acid chloride comprises any one or a combination of two or more of trimesoyl chloride, isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride, pyromellitic chloride, and 5-isocyanate-isophthaloyl chloride.
In some embodiments, the organic solvent comprises n-hexane, cyclohexane, benzene, toluene, or an isoparaffin solvent.
In some embodiments, the dispersion of carbon nanotubes or hydrophilic material modified carbon nanotubes is loaded onto the surface of the porous filter membrane by brushing, suction filtration, 3D printing, roll-to-roll imprinting, or spraying.
The embodiment of the invention also provides application of the reverse osmosis membrane in seawater desalination, brackish water desalination, drinking water purification, industrial sewage treatment or hemodialysis.
The embodiment of the invention also provides a membrane separation device, which comprises the reverse osmosis membrane.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The conditions used in the following examples may be further adjusted as necessary, and the conditions used in the conventional experiments are not generally indicated.
Example 1
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone microfiltration membrane with the aperture of 0.22 mu m by a brush coating method to obtain a carbon nanotube membrane with the thickness of about 80nm and the effective aperture of about 30 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.1g/L and trimesoyl chloride n-hexane solution with the concentration of 0.1 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone microfiltration membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 60 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) carrying out heat treatment on the membrane at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. SEM pictures of the carbon nanotube film intermediate layer loaded on the polyether sulfone micro-filtration membrane are shown in figures 2a-2b, AFM pictures are shown in figure 3, the porosity of the carbon nanotube film is high, the surface is smooth, and the roughness is 13.4 nm. The SEM photograph of the prepared polyamide membrane selective layer on the surface of the reverse osmosis membrane is shown in figure 4, the AFM photograph is shown in figure 5, the polyamide membrane is smooth in surface and 10.1nm in roughness, the polyamide membrane has the ultrathin characteristic, and the outline of the lower carbon nanotube is clear and visible.
The method for testing the performance of the reverse osmosis membrane comprises the following steps: the prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 2
The polydopamine modified double-wall carbon nano-tube is loaded on a polyethersulfone microfiltration membrane with the aperture of 0.22 mu m by a brush coating method to obtain a carbon nano-tube membrane with the thickness of about 80nm and the effective aperture of about 30 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 2g/L and trimesoyl chloride n-hexane solution with the concentration of 0.1 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone microfiltration membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 30 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was heat treated at 90 ℃ for 2 minutes, placed in a 0.1g/L NaClO solution for 30 seconds, and subsequently placed in 0.1g/L NaHCO3Taking out the membrane from the solution for 30 seconds, and washing the membrane with water to finally obtain a reverse membrane with a novel structure of a porous filter membrane supporting layer, a carbon nanotube membrane intermediate layer and a polyamide membrane selective layerA permeable membrane. The SEM photograph of the polyamide membrane selective layer on the surface of the prepared reverse osmosis membrane is shown in FIG. 6, the AFM photograph is shown in FIG. 7, the surface of the polyamide membrane is filled with a vesicle structure, and the roughness is 122.3 nm. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 3
The multi-wall carbon nano-tube modified by the sodium dodecyl benzene sulfonate is loaded on a nylon microfiltration membrane with the aperture of 0.45 mu m by a suction filtration method, so as to obtain the carbon nano-tube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.1g/L and trimesoyl chloride n-hexane solution with the concentration of 0.005 g/L. And (2) placing the carbon nanotube membrane loaded on the nylon microfiltration membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 60 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 4
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone membrane with the aperture of 0.45 mu m by a brush coating method to obtain the carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing a p-phenylenediamine aqueous solution with the concentration of 0.1g/L and preparing a m-phthaloyl chloro normal hexane solution with the concentration of 0.01 g/L. Placing the carbon nanotube membrane loaded on the polyether sulfone membrane in a p-phenylenediamine solution for 60 seconds, taking out the membrane, removing the excessive p-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane betweenPhthaloyl chloride solution for 60 seconds. And (3) taking out the membrane, cleaning the membrane by using normal hexane, and removing the redundant isophthaloyl dichloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 5
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone membrane with the aperture of 0.45 mu m by a brush coating method to obtain the carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing o-phenylenediamine aqueous solution with the concentration of 0.1g/L and preparing phthaloyl chloride n-hexane solution with the concentration of 0.01 g/L. And (3) placing the carbon nanotube membrane loaded on the polyether sulfone membrane in an o-phenylenediamine solution for 60 seconds, taking out the membrane, removing the excessive o-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a phthaloyl chloride solution for 60 seconds. And taking out the membrane, washing the membrane by using normal hexane, and removing the redundant phthaloyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 6
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone membrane with the aperture of 0.45 mu m by a brush coating method to obtain the carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing 0.1g/L p-ethylenediamine aqueous solution, preparing concentrateA phthaloyl chloride n-hexane solution with a degree of 0.01 g/L. And (3) placing the carbon nanotube membrane loaded on the polyether sulfone membrane in the p-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant p-ethylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in the terephthaloyl chloride solution for 60 seconds. And taking out the membrane, cleaning the membrane by using normal hexane, and removing the redundant phthaloyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 7
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone membrane with the aperture of 0.45 mu m by a brush coating method to obtain the carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. 0.1g/L of pyromellitic triamine aqueous solution and 0.01g/L of pyromellitic tetracarboxyl chloride n-hexane solution are prepared. And (3) placing the carbon nanotube membrane loaded on the polyether sulfone membrane in the pyromellitic triamine solution for 60 seconds, removing the redundant pyromellitic triamine solution on the surface of the membrane through an air knife after taking out the membrane, and then placing the membrane in the pyromellitic dianhydride solution for 120 seconds. And taking out the membrane, cleaning the membrane by using normal hexane, and removing the redundant pyromellitic chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 8
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone membrane with the aperture of 0.45 mu m by a brush coating method to obtain the carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing a 0.1 g/L5-sulfo metaphenylene diamine aqueous solution and a 0.01 g/L5-isocyanate-isophthaloyl dichloride n-hexane solution. Placing the carbon nanotube membrane loaded on the polyether sulfone membrane in a 5-sulfoacid group m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant 5-sulfoacid group m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a 5-isocyanate-isophthaloyl dichloride solution for 60 seconds. And taking out the membrane, cleaning the membrane by using normal hexane, and removing the redundant 5-isocyanate-isophthaloyl dichloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 9
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone membrane with the aperture of 0.45 mu m by a brush coating method to obtain the carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.1g/L and preparing 5-isocyanate-isophthaloyl dichloride n-hexane solution with the concentration of 0.01 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a 5-isocyanate-isophthaloyl chloride solution for 60 seconds. And taking out the membrane, cleaning the membrane by using normal hexane, and removing the redundant 5-isocyanate-isophthaloyl dichloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3The membrane is placed in 50g/L glycerin solution for 5 minutes after 30 minutes in the solution, the membrane is taken out and is washed by water and then is thermally treated at 90 ℃ for 2 minutes, and finally the porous filter membrane supporting layer, the carbon nanotube membrane middle layer and the polyamide membrane are obtainedA reverse osmosis membrane with a novel layer selection structure. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 10
Loading the polydopamine modified single-walled carbon nanotube on a polyethersulfone membrane with the aperture of 0.45 mu m by a brush coating method to obtain the carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing a 5-sulfoacid m-phenylenediamine aqueous solution with the concentration of 0.1g/L and preparing a benzene tricarboxychloride n-hexane solution with the concentration of 0.01 g/L. Placing the carbon nanotube membrane loaded on the polyether sulfone membrane in a 5-sulfoacid group m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant 5-sulfoacid group m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a benzene tricarbochloride solution for 60 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant benzene tricarbochloride solution on the surface of the membrane. The membrane was placed at 2g/LNa2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 11
Loading the polydopamine-modified single-walled carbon nanotube on a polyethersulfone microfiltration membrane with the aperture of 0.8 mu m by a roll-to-roll imprinting method to obtain a carbon nanotube membrane with the thickness of about 70nm and the effective aperture of about 40 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.2g/L and trimesoyl chloride n-hexane solution with the concentration of 0.01 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone microfiltration membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 60 seconds. Taking out the membrane, cleaning the membrane with n-hexane, and removing the superfluous trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 12
The double-wall carbon nano tube modified by the sodium dodecyl sulfate is loaded on a polyether sulfone microfiltration membrane with the aperture of 1 mu m by a 3D printing method, so that the carbon nano tube membrane with the thickness of about 80nm and the effective aperture of about 30nm is obtained. Preparing m-phenylenediamine aqueous solution with the concentration of 0.5g/L and trimesoyl chloride n-hexane solution with the concentration of 0.025 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone microfiltration membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 30 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was heat treated at 90 ℃ for 2 minutes, placed in a 0.1g/L NaClO solution for 30 seconds, and subsequently placed in 0.1g/L NaHCO3And (3) taking the membrane out of the solution for 30 seconds, and washing the membrane with water to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 13
The polydopamine modified multi-walled carbon nanotube is loaded on a zirconia micro-filtration membrane with the aperture of 1 mu m by a spraying method to obtain a carbon nanotube membrane with the thickness of about 100nm and the effective aperture of about 20 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.01g/L and trimesoyl chloride n-hexane solution with the concentration of 0.001 g/L. Placing a carbon nanotube membrane loaded on a polyether sulfone microfiltration membrane betweenThe solution of phenylenediamine is put into a solution of phenylenediamine for 60 seconds, the redundant solution of m-phenylenediamine on the surface of the membrane is removed by an air knife after the membrane is taken out, and then the membrane is put into a solution of trimesoyl chloride for 60 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed at 2g/LNa2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 2 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 14
The carboxylated single-walled carbon nanotube is loaded on a cellulose ester membrane with the aperture of 2 mu m by a spraying method to obtain the carbon nanotube membrane with the thickness of about 20nm and the effective aperture of about 100 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 10g/L and trimesoyl chloride n-hexane solution with the concentration of 1 g/L. The carbon nanotube film loaded on the cellulose ester film is placed in m-phenylenediamine solution for 60 seconds, the excessive m-phenylenediamine solution on the surface of the film is removed by an air knife after the film is taken out, and then the film is placed in trimesoyl chloride solution for 5 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 1 minute to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 15
And loading the polyvinylpyrrolidone modified multi-walled carbon nanotubes on a nylon membrane with the aperture of 10 mu m by a suction filtration method to obtain the carbon nanotube membrane with the thickness of about 500nm and the effective aperture of about 5 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.01g/L and trimesoyl chloride n-hexane solution with the concentration of 0.001 g/L. And (2) placing the carbon nanotube membrane loaded on the nylon microfiltration membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 60 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 100 ℃ for 0.5 minute to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 16
The dopamine-modified single-walled carbon nanotube is loaded on a polyvinylidene fluoride electrostatic spinning membrane with the aperture of 20 mu m by a spraying method to obtain the carbon nanotube membrane with the thickness of about 50 mu m and the effective aperture of about 1 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.01g/L and trimesoyl chloride n-hexane solution with the concentration of 0.001 g/L. Placing the carbon nanotube film loaded on the polyvinylidene fluoride electrostatic spinning film in a m-phenylenediamine solution for 600 seconds, taking out the film, removing the redundant m-phenylenediamine solution on the surface of the film through an air knife, and then placing the film in a trimesoyl chloride solution for 600 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3After 30 minutes in solution, the membrane was placed in a 50g/L glycerol solution for 5 minutes, taken out, washed with water and heat-treated at 60 ℃ for 30 minutes,finally obtaining the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 17
The carboxylated single-walled carbon nanotube modified by sodium dodecyl benzene sulfonate is loaded on a cellulose ester membrane with the aperture of 2 mu m by a spraying method, so that the carbon nanotube membrane with the thickness of about 20nm and the effective aperture of about 100nm is obtained. Preparing m-phenylenediamine aqueous solution with the concentration of 10g/L and trimesoyl chloride n-hexane solution with the concentration of 1 g/L. The carbon nanotube film loaded on the cellulose ester film is placed in m-phenylenediamine solution for 60 seconds, the excessive m-phenylenediamine solution on the surface of the film is removed by an air knife after the film is taken out, and then the film is placed in trimesoyl chloride solution for 5 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 1 minute to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 18
The carboxylated single-walled carbon nanotube modified by sodium dodecyl benzene sulfonate is loaded on a cellulose ester membrane with the aperture of 2 mu m by a spraying method, so that the carbon nanotube membrane with the thickness of about 20nm and the effective aperture of about 100nm is obtained. Preparing m-phenylenediamine aqueous solution with the concentration of 10g/L and trimesoyl chloride n-hexane solution with the concentration of 1 g/L. Placing the carbon nanotube film loaded on the cellulose ester film in m-phenylenediamine solution for 5s, taking out the film, and removing the surface of the film by an air knifeExcess m-phenylenediamine solution, and the membrane was then placed in trimesoyl chloride solution for 5 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 90 ℃ for 1 minute to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 19
Loading the single-walled carbon nanotube modified by the Trotion X-100 on a nylon membrane with the aperture of 0.45 mu m by a roll-to-roll imprinting method to obtain the carbon nanotube membrane with the thickness of about 200nm and the effective aperture of about 10 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.01g/L and trimesoyl chloride n-hexane solution with the concentration of 0.001 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone microfiltration membrane in a m-phenylenediamine solution for 60 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 600 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 40 ℃ for 60 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 20
Loading the single-walled carbon nanotube modified by the Trotion X-100 on a nylon membrane with the aperture of 0.45 mu m by a roll-to-roll imprinting method to obtain the carbon nanotube membrane with the thickness of about 200nm and the effective aperture of about 10 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.01g/L and trimesoyl chloride n-hexane solution with the concentration of 10 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone microfiltration membrane in a m-phenylenediamine solution for 600 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 60 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3And (3) soaking in the solution for 30 minutes, then placing the membrane in a 50g/L glycerol solution for 5 minutes, taking out the membrane, washing with water, and then carrying out heat treatment at 40 ℃ for 60 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane intermediate layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Example 21
Loading the single-walled carbon nanotube modified by the Trotion X-100 on a nylon membrane with the aperture of 0.45 mu m by a roll-to-roll imprinting method to obtain the carbon nanotube membrane with the thickness of about 200nm and the effective aperture of about 10 nm. Preparing m-phenylenediamine aqueous solution with the concentration of 0.01g/L and trimesoyl chloride n-hexane solution with the concentration of 0.001 g/L. And (2) placing the carbon nanotube membrane loaded on the polyether sulfone microfiltration membrane in a m-phenylenediamine solution for 600 seconds, taking out the membrane, removing the redundant m-phenylenediamine solution on the surface of the membrane through an air knife, and then placing the membrane in a trimesoyl chloride solution for 600 seconds. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. And (3) taking out the membrane, washing the membrane by using normal hexane, and removing the redundant trimesoyl chloride solution on the surface of the membrane. The membrane was placed in 2g/L Na2CO3After 30 minutes in solution, the membrane was placed in 50g/L glycerol solution for 5 minutes, removed and washed with water at 40 deg.CAnd performing heat treatment for 60 minutes to finally obtain the reverse osmosis membrane with the novel structure of the porous filter membrane supporting layer, the carbon nanotube membrane middle layer and the polyamide membrane selective layer. The prepared reverse osmosis membrane was placed in a standard reverse osmosis test apparatus and 2000ppm NaCl solution was separated at 25 deg.C under a pressure of 1.6MPa and a pH of 7, and the flux and salt rejection were recorded as shown in Table 1.
Table 1 below shows the results of performance tests of the reverse osmosis membranes obtained in examples 1 to 21.
Figure BDA0001879542710000141
Figure BDA0001879542710000151
Table 1.
As can be seen from Table 1, the reverse osmosis membrane of the invention can separate 2000ppm NaCl solution under the conditions of 25 ℃, 1.6MPa of pressure and 7 of pH value, and the water flux can reach 50-100Lm-2h-1The NaCl desalting rate reaches more than 97 percent.
The reverse osmosis membrane can be applied to the fields of seawater desalination, brackish water desalination, drinking water purification, industrial sewage treatment or hemodialysis and the like. And can be applied to a membrane separation device.
In addition, the inventor also carries out corresponding tests by using other process conditions and the like listed in the foregoing to replace the corresponding process conditions in the examples 1 to 21, and the contents to be verified are similar to the products of the examples 1 to 21. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by examples 1 to 21 as representative examples.
It should be noted that, in the present document, in a general case, an element defined by the phrase "includes.
It should be understood that the above-mentioned examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and to implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (14)

1. A reverse osmosis membrane characterized by: the reverse osmosis membrane comprises a porous filter membrane supporting layer, a carbon nanotube membrane middle layer and a polyamide membrane selection layer which are sequentially arranged.
2. A reverse osmosis membrane according to claim 1 wherein: the porous filter membrane support layer comprises a porous filter membrane; preferably, the porous filter membrane is selected from a microfiltration membrane or an ultrafiltration membrane; preferably, the pore diameter of the porous filter membrane is 2 nm-20 μm; preferably, the material of the porous filter membrane is selected from any one of a polymer membrane, an inorganic membrane and an organic-inorganic hybrid membrane.
3. A reverse osmosis membrane according to claim 1 wherein: the carbon nano tube film middle layer is a reticular film formed by alternately stacking a plurality of carbon nano tubes; preferably, the carbon nanotubes include any one or a combination of two or more of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled carbon nanotubes modified by a hydrophilic material, double-walled carbon nanotubes modified by a hydrophilic material and multi-walled carbon nanotubes modified by a hydrophilic material; preferably, the thickness of the carbon nanotube film intermediate layer is 20nm to 50 μm, and the pore diameter is 1nm to 100 nm.
4. A reverse osmosis membrane according to claim 1 wherein: the polyamide membrane selection layer comprises a polyamide membrane, and the polyamide membrane is prepared from polyamine and polyacyl chloride through interfacial polymerization reaction.
5. A method for producing a reverse osmosis membrane according to any one of claims 1 to 4, characterized by comprising:
(1) loading the dispersion liquid of the carbon nano tubes modified by the carbon nano tubes or the hydrophilic materials on the surface of the porous filter membrane to obtain a reticular carbon nano tube membrane formed by alternately stacking the carbon nano tubes or the carbon nano tubes modified by the hydrophilic materials;
(2) dissolving polyamine in water to prepare a water phase solution with the concentration of 0.01-10 g/L; dissolving polybasic acyl chloride in an organic solvent to prepare an organic phase solution with the concentration of 0.001-10 g/L;
(3) contacting the surface of the carbon nanotube film with the aqueous phase solution, and removing the aqueous phase solution remained on the surface of the carbon nanotube film after the aqueous phase solution completely wets the surface of the carbon nanotube film; then contacting the surface of the carbon nano tube membrane contacted with the aqueous phase solution with the organic phase solution, and carrying out interfacial polymerization reaction on polyamine and polybasic acyl chloride on the surface of the carbon nano tube membrane to generate a polyamide membrane;
(4) removing redundant polybasic acyl chloride on the surface of the obtained polyamide membrane to obtain the reverse osmosis membrane.
6. The method of claim 5, wherein: in the step (3), the surface of the carbon nanotube film is contacted with the aqueous phase solution in a manner of immersion or coating for more than 5 seconds; and contacting the surface of the carbon nanotube film contacted with the aqueous phase solution with the organic phase solution in a manner of immersing or coating for 5-600 seconds.
7. The method according to claim 5, wherein the step (4) specifically comprises: removing redundant polybasic acyl chloride on the surface of the polyamide membrane, carrying out heat treatment at 40-100 ℃ for 0-60 min, and then carrying out post-treatment to obtain the reverse osmosis membrane.
8. The method of claim 5, wherein: the hydrophilic material in the step (1) comprises dopamine, polydopamine, tannic acid, polyethyleneimine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, polyvinylpyrrolidone or Trotion X-100.
9. The method of claim 5, wherein: the polyamine comprises any one or the combination of more than two of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, p-ethylenediamine, trimesamine and 5-sulfoacid m-phenylenediamine.
10. The method of claim 5, wherein: the polybasic acyl chloride comprises one or the combination of more than two of trimesoyl chloride, isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride, pyromellitic chloride and 5-isocyanate-isophthaloyl chloride.
11. The method of claim 5, wherein: the organic solvent comprises n-hexane, cyclohexane, benzene, toluene or an isoparaffin solvent.
12. The method of claim 5, wherein: and loading the dispersion liquid of the carbon nano tubes modified by the carbon nano tubes or the hydrophilic material on the surface of the porous filter membrane by adopting a brushing mode, a suction filtration mode, a 3D printing mode, a roll-to-roll imprinting mode or a spraying mode.
13. Use of a reverse osmosis membrane according to any one of claims 1 to 4 in sea water desalination, brackish water desalination, drinking water purification, industrial sewage treatment or haemodialysis.
14. A membrane separation device comprising the reverse osmosis membrane according to any one of claims 1 to 4.
CN201811420891.0A 2018-11-26 2018-11-26 Reverse osmosis membrane and preparation method and application thereof Pending CN111214965A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112403288A (en) * 2020-12-11 2021-02-26 江苏泷膜环境科技有限公司 High-strength pollution-resistant composite reverse osmosis membrane and preparation method thereof
CN112999898A (en) * 2021-02-08 2021-06-22 青岛科技大学 High-flux nanofiltration membrane capable of realizing monovalent/divalent ion selective separation and preparation method thereof
CN113121859A (en) * 2021-04-22 2021-07-16 哈尔滨工业大学 Preparation method of electropolymerized polydopamine-carbon nanotube composite membrane
CN113244794A (en) * 2021-05-11 2021-08-13 燕山大学 Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution
CN113324969A (en) * 2021-04-06 2021-08-31 金陵科技学院 Metal/carbon nanotube composite filter membrane, and manufacturing method and application thereof
CN113491955A (en) * 2021-06-04 2021-10-12 中国石油大学(华东) Composite membrane with heterostructure separation layer and preparation method thereof
CN113663530A (en) * 2021-08-24 2021-11-19 北京工业大学 MoS-containing2Polyamide ceramic composite nanofiltration membrane in middle layer and preparation method thereof
CN113684371A (en) * 2021-07-29 2021-11-23 中国科学院金属研究所 Method for efficiently recovering gold based on poly-tannic acid coated carbon nanotube composite membrane
CN113713640A (en) * 2021-09-14 2021-11-30 江苏拓邦环保科技有限公司 High-flux alkali-washing-resistant reverse osmosis membrane and preparation method thereof
CN114053874A (en) * 2021-11-04 2022-02-18 浙江工业大学 High-flux polyamide/metal organic framework composite reverse osmosis membrane
CN114177781A (en) * 2021-12-14 2022-03-15 湖南澳维科技股份有限公司 Preparation method of reverse osmosis composite membrane and obtained reverse osmosis composite membrane
CN114471183A (en) * 2020-11-11 2022-05-13 沃顿科技股份有限公司 Method for producing separation membrane and separation membrane produced thereby

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102802772A (en) * 2009-06-18 2012-11-28 波音公司 Methods And Systems For Incorporation Carbon Nanotubes Into Thin Film Composite Reverse Osmosis Membranes
KR20140073354A (en) * 2012-12-06 2014-06-16 도레이케미칼 주식회사 Polyamide composite membrane having high quality and manufacturing method thereof
CN104174299A (en) * 2014-07-30 2014-12-03 中国海洋大学 High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof
CN105289322A (en) * 2015-09-25 2016-02-03 天津工业大学 Composite forward osmosis membrane based on superthin support layer and preparation method thereof
CN106552514A (en) * 2016-11-11 2017-04-05 北京碧水源膜科技有限公司 A kind of integral and intelligent clear water faucet specific complex NF membrane and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102802772A (en) * 2009-06-18 2012-11-28 波音公司 Methods And Systems For Incorporation Carbon Nanotubes Into Thin Film Composite Reverse Osmosis Membranes
KR20140073354A (en) * 2012-12-06 2014-06-16 도레이케미칼 주식회사 Polyamide composite membrane having high quality and manufacturing method thereof
CN104174299A (en) * 2014-07-30 2014-12-03 中国海洋大学 High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof
CN105289322A (en) * 2015-09-25 2016-02-03 天津工业大学 Composite forward osmosis membrane based on superthin support layer and preparation method thereof
CN106552514A (en) * 2016-11-11 2017-04-05 北京碧水源膜科技有限公司 A kind of integral and intelligent clear water faucet specific complex NF membrane and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
（葡）阿丰索等著，许振良等译: "《绿色分离过程 基础与应用》", 31 May 2008, 上海：华东理工大学出版社 *
徐昳荃等: "《文化丝绸》", 31 July 2016, 苏州大学出版社 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471183A (en) * 2020-11-11 2022-05-13 沃顿科技股份有限公司 Method for producing separation membrane and separation membrane produced thereby
CN114471183B (en) * 2020-11-11 2023-03-14 沃顿科技股份有限公司 Method for producing separation membrane and separation membrane produced thereby
CN112403288A (en) * 2020-12-11 2021-02-26 江苏泷膜环境科技有限公司 High-strength pollution-resistant composite reverse osmosis membrane and preparation method thereof
CN112999898A (en) * 2021-02-08 2021-06-22 青岛科技大学 High-flux nanofiltration membrane capable of realizing monovalent/divalent ion selective separation and preparation method thereof
CN113324969A (en) * 2021-04-06 2021-08-31 金陵科技学院 Metal/carbon nanotube composite filter membrane, and manufacturing method and application thereof
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CN113121859A (en) * 2021-04-22 2021-07-16 哈尔滨工业大学 Preparation method of electropolymerized polydopamine-carbon nanotube composite membrane
CN113244794A (en) * 2021-05-11 2021-08-13 燕山大学 Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution
CN113491955A (en) * 2021-06-04 2021-10-12 中国石油大学(华东) Composite membrane with heterostructure separation layer and preparation method thereof
CN113684371A (en) * 2021-07-29 2021-11-23 中国科学院金属研究所 Method for efficiently recovering gold based on poly-tannic acid coated carbon nanotube composite membrane
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