CN112973479A - High-flux reverse osmosis membrane and preparation method and application thereof - Google Patents
High-flux reverse osmosis membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 113
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 74
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 68
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 67
- 239000008346 aqueous phase Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004952 Polyamide Substances 0.000 claims abstract description 34
- 229920002647 polyamide Polymers 0.000 claims abstract description 34
- 239000012074 organic phase Substances 0.000 claims abstract description 33
- 230000004907 flux Effects 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 229920000768 polyamine Polymers 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 10
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 10
- 230000005501 phase interface Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 87
- 210000004379 membrane Anatomy 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 17
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 13
- 238000010612 desalination reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000013535 sea water Substances 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000704 physical effect Effects 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000011852 carbon nanoparticle Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a high-flux reverse osmosis membrane and a preparation method and application thereof. The preparation method comprises the following steps: and taking the surface of the basement membrane as an aqueous phase-oil phase interface of an aqueous phase solution containing polyamine monomers, carboxylic acid carbon nano tubes and polyvinyl alcohol and an organic phase solution containing polybasic acyl chloride, and carrying out interfacial polymerization reaction on the polyamine monomers and the polybasic acyl chloride at the interface so as to form an ultrathin polyamide separation layer on the surface of the basement membrane, thereby obtaining the high-flux reverse osmosis membrane. According to the invention, the carboxylated carbon nanotubes and the polyvinyl alcohol are introduced into the water phase, so that the polymerization reaction is carried out in a limited space, the salt rejection rate and the water flux of the prepared high-flux reverse osmosis membrane are greatly improved, the use amount of the carboxylated carbon nanotubes and the polyvinyl alcohol is very small, the cost is greatly reduced, and meanwhile, the reverse osmosis membrane has better hydrophilicity and strength.
Description
Technical Field
The invention belongs to the technical field of reverse osmosis membranes, particularly relates to a high-flux reverse osmosis membrane and a preparation method and application thereof, and particularly relates to a high-flux reverse osmosis membrane based on carboxylated carbon nanotubes and polyvinyl alcohol and a preparation method and application thereof.
Background
The reverse osmosis membrane (RO) separation technology is widely applied to the fields of sea water desalination, brackish water desalination, sewage treatment and the like, and generally comprises three parts, namely non-woven fabrics, a polysulfone porous supporting layer and a compact separation layer. The non-woven fabric and polysulfone porous supporting layer provide good thermal stability and mechanical property, the polyamide compact separation layer plays a role in separation, and the research on the composite reverse osmosis membrane mainly focuses on the three processes of the supporting layer, the interfacial polymerization separation layer and the post-treatment. For the composite membrane, the permeation flux and salt rejection rate mainly depend on the surface ultrathin dense layer, and the preparation of ultrathin dense separation layer by interfacial polymerization method is a hot spot of research.
At present, the aromatic polyamide reverse osmosis composite membrane is mainly prepared by the interfacial polymerization reaction of m-phenylenediamine (MPD) and trimesoyl chloride (TMC), and the polyamide reverse osmosis composite membrane prepared by the interfacial polymerization method has the following problems: (1) the mutual restriction between high desalination rate and high water flux; (2) the pollution resistance is poor; (3) poor chlorine resistance, etc.
The polyamide reverse osmosis composite membrane prepared by the interfacial polymerization method often has the problem of mutual restriction between the desalination rate and the water flux. Therefore, it is an urgent problem to improve both the desalination rate and the water flux of the reverse osmosis composite membrane.
Disclosure of Invention
The invention mainly aims to provide a high-flux reverse osmosis membrane and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a high-flux reverse osmosis membrane, which comprises the following steps:
providing a base film;
and taking the surface of the basement membrane as a water phase-oil phase interface of an aqueous phase solution containing polyamine monomers, carboxylic acid carbon nano tubes and polyvinyl alcohol (PVA) and an organic phase solution containing polybasic acyl chloride, and carrying out interfacial polymerization reaction on the polyamine monomers and the polybasic acyl chloride at the interface so as to form an ultrathin polyamide separation layer on the surface of the basement membrane, thereby obtaining the high-flux reverse osmosis membrane.
The embodiment of the invention also provides the high-flux reverse osmosis membrane prepared by the method.
The embodiment of the invention also provides application of the high-flux reverse osmosis membrane in the fields of seawater desalination, brackish water desalination or sewage treatment.
In the invention, the hydroxyl group in PVA and the carboxylic carbon nanotube are bonded together through hydrogen bond to achieve the synergistic effect: (1) the water flux of the reverse osmosis membrane is greatly improved by utilizing a smooth internal water channel of the carboxylated carbon nano tube and a nano gap between the carboxylated carbon nano tube and polyamide, the water flux of the reverse osmosis membrane is greatly improved by shortening a diffusion path, and the carboxylated carbon nano tube has very high specific surface area and surface energy and is very easy to agglomerate due to strong van der Waals force, if the carbon nano tube is directly added into an interfacial polymerization water phase, the m-phenylenediamine in the water phase has low solid content, and the carboxylated carbon nano tube is very easy to agglomerate, so that the polyamide membrane has defects; (2) both the carboxylated carbon nanotube and the PVA have hydrophilic groups, so that the hydrophilicity of the membrane can be obviously improved; (3) the PVA has a regular structure and high mechanical strength, and is combined with the carboxylic carbon nanotube, so that the strength of the polyamide membrane is greatly improved; (4) the consumption of the carboxylic acid carbon nano tube and the PVA is less, and the cost is greatly reduced while the performance reverse osmosis performance is improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) the high-flux reverse osmosis membrane prepared by the invention has excellent separation performance, greatly improves the desalination rate and water flux, simultaneously has little use amount of the carboxylic acid carbon nano tube and PVA, and greatly reduces the cost. Wherein, when the content of the carboxylated carbon nano tube in the aqueous phase solution is 0.03 weight percent and the content of the PVA polymer is 0.05 weight percent, the flux of the reverse osmosis membrane is determined by the flux of the reverse osmosis membrane when the carboxylated carbon nano tube and the PVA polymer are not added39.0L/m2h is increased to 52.7GPD, the salt rejection rate of NaCl solution is increased from 97.5% to 98.7% by 1.4 times, and the effect is obvious;
(2) according to the invention, the performance of the reverse osmosis membrane is improved by adding the nano particles (the carboxylated carbon nanotubes) and the PVA polymer into the aqueous phase solution, on one hand, the carboxylated carbon nanotubes are embedded into the ultrathin Polyamide (PA) separation layer, and the smooth internal water channel of the carboxylated carbon nanotubes and the nano gaps between the carboxylated carbon nanotubes and the PVA polymer are utilized, so that the diffusion path is shortened, and the flux of the reverse osmosis membrane is greatly improved; on the other hand, the PVA polymer is added to increase the viscosity of the water phase, which is beneficial to reducing the defects caused by nano particles in the process of interfacial polymerization reaction, meanwhile, m-phenylenediamine (MPD) in the water phase solution is combined with the hydroxyl of the PVA through hydrogen bonds to form a reaction active chain guided by a macromolecular chain, the diffusion of amine to an organic phase is inhibited, the polymerization reaction is carried out in a limited space, the thickness of the polyamide separation layer is reduced, the density is increased, and the hydrophilicity of the surface of the polyamide separation layer can be further enhanced by the hydrophilic groups contained in the carboxylated carbon nano tube and the PVA.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a method for preparing a high flux reverse osmosis membrane, which includes:
providing a base film;
and taking the surface of the basement membrane as an aqueous phase-oil phase interface of an aqueous phase solution containing polyamine monomers, carboxylic acid carbon nano tubes and polyvinyl alcohol and an organic phase solution containing polybasic acyl chloride, and carrying out interfacial polymerization reaction on the polyamine monomers and the polybasic acyl chloride at the interface so as to form an ultrathin polyamide separation layer on the surface of the basement membrane, thereby obtaining the high-flux reverse osmosis membrane.
In some more specific embodiments, the preparation method specifically comprises:
fully soaking the surface of the base film for 1-5min by using the aqueous phase solution; and the number of the first and second groups,
and fully infiltrating the surface of the basement membrane with the organic phase solution, so that the polyamine monomer and the polyacyl chloride are subjected to interfacial polymerization reaction at the interface for 10-30s at room temperature.
In some more specific embodiments, the preparation method comprises: mixing polyamine monomer, polyvinyl alcohol and water, stirring for 2-5h at 85-95 ℃, then adding carboxylic acid carbon nano tubes and an acid absorbent, uniformly mixing to form the aqueous phase solution, and adjusting the pH value of the aqueous phase solution to 7-9.
Further, the acid absorbent includes any one or a combination of two or more of sodium hydroxide, triethylamine, and pyridine, and is not limited thereto.
Further, the preparation method specifically comprises the following steps: mixing polyamine monomer, PVA and water, stirring at 85-95 ℃ for 2-5h, then adding carboxylic acid carbon nano tubes and an acid absorbent, uniformly mixing to form the aqueous phase solution, and adjusting the pH value of the aqueous phase solution to 7-9.
Further, the length of the carboxylated carbon nanotube is 0.5-2 mu m.
Further, the carboxylated carbon nanotube is a one-dimensional hollow tubular nano material formed by rolling a graphite sheet layer.
Further, the molecular weight of the polyvinyl alcohol is 25000-30000 Da.
Further, the polyamine monomer includes any one or a combination of two of m-phenylenediamine and ethylenediamine, and is not limited thereto.
Further, the concentration of polyamine monomer in the aqueous phase solution is 1-5% by weight.
Further, the concentration of the carboxylated carbon nanotubes in the aqueous phase solution is 0.01 to 0.05 weight percent.
Further, the concentration of the polyvinyl alcohol in the aqueous phase solution is 0.05-0.1 wt%.
In some more specific embodiments, the preparation method specifically comprises: and uniformly mixing the polyacyl chloride and the organic solvent to form the organic phase solution.
Further, the organic solvent includes any one of n-hexane, cyclohexane or a combination of both, and is not limited thereto.
Further, the polybasic acid chloride includes trimesoyl chloride, and is not limited thereto.
Further, the concentration of the polybasic acyl chloride in the organic phase solution is 0.1-0.5 wt%.
In some more specific embodiments, the preparation method comprises: and immersing the base membrane in the aqueous phase solution for 1-5min, removing the aqueous phase solution and redundant bubbles remained on the base membrane, then immersing in the organic phase solution for 10-30s, performing interfacial polymerization reaction at room temperature to form an ultrathin polyamide separation layer, taking out and drying to obtain the high-flux reverse osmosis membrane.
In some more specific embodiments, the preparation method further comprises: and after the interfacial polymerization reaction is finished, drying the base film with the surface undergoing the interfacial polymerization reaction at the temperature of 45-75 ℃ for 5-10min, and curing and forming to form the ultrathin polyamide separation layer.
Further, the base film includes a polysulfone base film, and is not limited thereto.
In some more specific embodiments, the preparation method further comprises: and (3) rolling the polysulfone base film by using a rubber roller to remove the residual excessive aqueous phase solution and bubbles in the polysulfone base film.
In some more specific embodiments, the preparation method further comprises: before the aqueous phase solution is prepared, the carboxylic acid carbon nano tube is placed in a vacuum oven 100 ℃ and 140 ℃ for drying for 10-14h to constant weight, and is moved to a dryer to be cooled to room temperature for later use.
In some more specific embodiments, the method for preparing the high flux reverse osmosis membrane based on carbon nanotubes and PVA comprises:
(1) preparation of an aqueous phase: mixing polyamine monomer, PVA and water, stirring at 85-95 ℃ for 2-5h to prepare an aqueous phase solution, adding carboxylic acid carbon nano tubes to disperse the carbon nano tubes uniformly, adding acid absorbent sodium hydroxide, triethylamine, pyridine and the like, and adjusting the pH value of the aqueous phase to 7.0-9.0;
(2) configuration of the organic phase: adding trimesoyl chloride into organic solvents such as normal hexane, cyclohexane and the like to prepare organic phase solution;
(3) preparing a reverse osmosis membrane: immersing the polysulfone basal membrane into the water phase solution for 1-5min, taking out, draining to remove surface bubbles and redundant water phase solution, immersing into the organic phase solution for 10-30s, carrying out interfacial polymerization reaction, taking out, and drying to finish the preparation of the reverse osmosis membrane.
In another aspect of the embodiments of the present invention, there is also provided a high flux reverse osmosis membrane prepared by the foregoing method.
Further, the high-flux reverse osmosis membrane comprises a base membrane and an ultrathin polyamide separation layer which are sequentially stacked, wherein carboxylic carbon nanotubes and polyvinyl alcohol polymer are embedded in the ultrathin polyamide separation layer, and the carboxylic carbon nanotubes and the polyvinyl alcohol are combined through hydrogen bonds.
Further, the thickness of the ultra-thin polyamide separation layer is 150-250nm, and the density range is 1.1-1.2g/cm3。
Furthermore, the high-flux reverse osmosis membrane has the water flux of 52.7L/m under the conditions of 15.5bar, 2000ppmNaCl water solution, 25 ℃ and pH value of 7-82h, the salt rejection rate reaches 98.7%.
Further, the contact angle between the high-flux reverse osmosis membrane and water is 0-47 degrees.
In another aspect, the embodiment of the invention also provides the application of the high flux reverse osmosis membrane in the fields of sea water desalination, brackish water desalination or sewage treatment.
In the invention, inorganic particles (carboxylic carbon nano tubes) are introduced into an organic network, so that the distribution and the network structure of membrane pores can be improved and modified, the hydrophilicity, the roughness and the like of the membrane surface are adjusted, an ordered water channel is established, and the flux, the desalination rate, the stain resistance and the like of the membrane are improved; the molecular chain of polyvinyl alcohol (PVA) contains a large number of hydroxyl groups, so that the PVA has high hydrophilicity, has strong interaction with MPD, can inhibit diffusion of MPD to an organic phase, weakens the concentration gradient of MPD, inhibits the formation of a concave-convex structure on the surface of a Polyamide (PA) film, and reduces the surface roughness of the film; meanwhile, the reduction of the diffusion speed of the water phase is beneficial to reducing the thickness of the separation layer; in addition, hydrogen bonds are formed between the PVA polymer and the polyamide to play a role of a cross-linking agent, so that the cross-linking degree of the polyamide polymer is increased, the compactness is increased, and the flux of the reverse osmosis membrane is improved to a certain extent on the premise of not reducing the desalting performance.
The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
A preparation method of a high-flux reverse osmosis membrane based on a carboxylated carbon nanotube and PVA comprises the following steps:
(1) pretreatment of nano particles: placing the carboxylated carbon nanotube in a vacuum oven, drying at 120 ℃ for 12h to constant weight, and transferring to a dryer to cool to room temperature for later use;
(2) preparation of aqueous phase solution: preparing an aqueous solution containing m-phenylenediamine and PVA, wherein the concentrations of the m-phenylenediamine and the PVA are respectively 1 wt% and 0.05 wt%, heating to 90 ℃, and stirring for 3 hours; slowly adding 0.01 wt% of carboxylic acid carbon nano tube, dropwise adding sodium hydroxide to adjust the pH value of the aqueous solution to 8.5, and performing ultrasonic treatment for 1h at room temperature to obtain an aqueous phase solution;
(3) preparation of organic phase solution: dissolving trimesoyl chloride in cyclohexane to form an organic phase solution, wherein the concentration of the trimesoyl chloride is 0.1 wt%, and fully stirring and dissolving to obtain the organic phase solution;
(4) soaking a polysulfone base membrane in an aqueous phase solution for 3min, contacting the aqueous phase solution only on the front surface of the membrane, taking out the soaked membrane, slightly rolling the surface of the membrane for 2 times by using a rubber roller, removing redundant bubbles and the aqueous phase solution on the surface, then contacting the membrane with an organic phase solution for 20s, completing interfacial polymerization reaction, finally drying the membrane in a vacuum oven at 60 ℃ for 8min, completing solidification and shaping of an ultrathin polyamide separation layer, preparing the high-flux reverse osmosis membrane based on the carbon nano tube and PVA, and storing the membrane in deionized water.
The reverse osmosis membrane containing the carboxylated carbon nanotubes and the PVA polymer is subjected to performance characterization, and the data are shown in Table 1.
Example 2
The amount of the carboxylated carbon nanotubes in the aqueous phase solution in the step (2) is different from that in the embodiment 1, the other steps are the same as the embodiment 1, and the amount of the carboxylated carbon nanotubes is 0.03 wt%; the characterization data of the properties of the prepared reverse osmosis membrane are shown in table 1.
Example 3
The amount of the carboxylated carbon nanotubes in the aqueous phase solution in the step (2) is different from that in the embodiment 1, the other steps are the same as in the embodiment 1, and the amount of the carboxylated carbon nanotubes is 0.05 wt%; the characterization data of the properties of the prepared reverse osmosis membrane are shown in table 1.
Comparative example 1
The same as example 1 except that no carboxylated carbon nanotubes and no PVA polymer were added to the water phase; the characterization data of the properties of the prepared reverse osmosis membrane are shown in table 1.
Comparative example 2
The aqueous phase was not supplemented with carboxylated carbon nanotubes, and the remainder was the same as in example 1.
TABLE 1 Water flux and salt rejection of reverse osmosis membranes prepared in examples 1 to 3 and comparative examples 1 to 2
As can be seen from comparative examples 1-2, by adding a small amount of PVA to the aqueous phase, the flux and salt rejection of the reverse osmosis membrane can be improved.
It can be seen from examples 1-3 that the flux can be greatly increased without decreasing the salt rejection rate by adding a suitable amount of carboxylated carbon nanotubes to the reverse osmosis membrane.
Example 4
A preparation method of a high-flux reverse osmosis membrane based on a carboxylated carbon nanotube and PVA comprises the following steps:
(1) pretreatment of nano particles: placing the carboxylated carbon nanotube in a vacuum oven, drying at 120 ℃ for 12h to constant weight, and transferring to a dryer to cool to room temperature for later use;
(2) preparation of aqueous phase solution: preparing an aqueous solution containing m-phenylenediamine and PVA, wherein the concentrations of the m-phenylenediamine and the PVA are respectively 1 wt% and 0.07 wt%, heating to 90 ℃, and stirring for 3 hours; slowly adding 0.03 wt% of carboxylic acid carbon nano tube, dropwise adding sodium hydroxide to adjust the pH value of the aqueous solution to 8.5, and performing ultrasonic treatment for 1h at room temperature to obtain an aqueous phase solution;
(3) preparation of organic phase solution: dissolving trimesoyl chloride in cyclohexane to form an organic phase solution, wherein the concentration of the trimesoyl chloride is 0.1 wt%, and fully stirring and dissolving to obtain the organic phase solution;
(4) soaking a polysulfone base membrane in an aqueous phase solution for 3min, contacting the aqueous phase solution only on the front surface of the membrane, taking out the soaked membrane, slightly rolling the surface of the membrane for 2 times by using a rubber roller, removing redundant bubbles and the aqueous phase solution on the surface, then contacting the membrane with an organic phase solution for 20s, completing interfacial polymerization reaction, finally drying the membrane in a vacuum oven at 60 ℃ for 8min, completing solidification and shaping of an ultrathin polyamide separation layer, preparing the high-flux reverse osmosis membrane based on the carbon nano tube and PVA, and storing the membrane in deionized water.
The reverse osmosis membrane containing the carboxylated carbon nanotubes and the PVA polymer is subjected to performance characterization, and the data are shown in Table 2.
Example 5
The amount of PVA polymer used in the aqueous phase solution of only step (2) was different from that of example 4, and the other was the same as that of example 4, and the amount of PVA polymer used was 0.1% by weight.
Comparative example 3
The same procedure as in example 4 was repeated except that the PVA polymer content in the water phase was 0.
TABLE 2 Water flux and salt rejection of reverse osmosis membranes prepared in example 2/4/5 and comparative example 1/3
As can be seen from comparative examples 1 and 3, the flux and the salt rejection rate of the reverse osmosis membrane can be improved simultaneously by adding a proper amount of carboxylic carbon nano tubes into the water phase.
As can be seen from examples 2, 4 and 5, the addition of a proper amount of PVA polymer to the aqueous phase can significantly improve the flux and salt rejection rate of the reverse osmosis membrane, but the addition of an excessive amount of PVA will result in a decrease in salt rejection rate.
Comparative example 4
The aqueous phase solution was added with 0.03% carboxylated carbon nanotubes and then 0.05% PVA polymer by weight, and the rest of the procedure was the same as in example 2.
Comparative example 5
The same procedure as in example 2 was repeated except that 0.03 wt% of the carboxylated carbon nanotube and 0.05 wt% of the PVA polymer were added to the aqueous solution at the same time.
The effect of the order of addition of the carboxylated carbon nanotubes and PVA polymer in the aqueous phase on the performance of the reverse osmosis membrane is shown in table 3.
TABLE 3 Water flux and salt rejection of reverse osmosis membranes prepared in example 2 and comparative examples 4 to 5
From the data, it can be seen that the salt rejection of the reverse osmosis membrane is suddenly reduced to 65.4% by adding the carboxylated carbon nanotubes and the PVA polymer into the interfacial polymerization water phase at the same time, and the salt rejection is only 72.1%. The main reason is that the carbon nano-particles have high specific surface area and surface energy, and strong van der Waals force exists among the carbon nano-particles, so that the carbon nano-particles are easy to agglomerate, if the carbon nano-particles are directly added into an interfacial polymerization water phase, the m-phenylenediamine solid content in the water phase is low, and the carbon nano-particles are easy to agglomerate, so that a PA layer generates defects, and meanwhile, the difference of water contact angles at different positions is large, and the defects are also caused by ion agglomeration. Therefore, the PVA polymer is added firstly, and then the carboxylated carbon nano-tube nano-particles are added, so that the PVA polymer and the carboxylated carbon nano-tube nano-particles are bonded together by hydrogen bonds, and the dispersion effect of the nano-particles is improved.
Example 6
A preparation method of a high-flux reverse osmosis membrane based on a carboxylated carbon nanotube and PVA comprises the following steps:
(1) pretreatment of nano particles: drying the carboxylated carbon nanotubes in a vacuum oven at 100 ℃ for 14h to constant weight, and transferring to a dryer to cool to room temperature for later use;
(2) preparation of aqueous phase solution: preparing an aqueous solution containing m-phenylenediamine and PVA, wherein the concentrations of the m-phenylenediamine and the PVA are respectively 5 wt% and 0.1 wt%, heating to 85 ℃, and stirring for 5 hours; slowly adding 0.05 wt% of carboxylic acid carbon nano tube, dropwise adding sodium hydroxide to adjust the pH value of the aqueous solution to 9, and performing ultrasonic treatment for 1h at room temperature to obtain an aqueous phase solution;
(3) preparation of organic phase solution: dissolving trimesoyl chloride in n-hexane to form an organic phase solution, wherein the concentration of the trimesoyl chloride is 0.5 wt%, and fully stirring and dissolving to obtain the organic phase solution;
(4) soaking a polysulfone base membrane in an aqueous phase solution for 1min, contacting the aqueous phase solution only on the front surface of the membrane, taking out the soaked membrane, slightly rolling the surface of the membrane for 2 times by using a rubber roller, removing redundant bubbles and the aqueous phase solution on the surface, then contacting the membrane with an organic phase solution for 10s, completing interfacial polymerization reaction, finally drying the membrane in a vacuum oven at 75 ℃ for 5min, completing solidification and shaping of an ultrathin polyamide separation layer, preparing the high-flux reverse osmosis membrane based on the carbon nano tube and PVA, and storing the membrane in deionized water.
Example 7
A preparation method of a high-flux reverse osmosis membrane based on a carboxylated carbon nanotube and PVA comprises the following steps:
(1) pretreatment of nano particles: drying the carboxylated carbon nanotubes in a vacuum oven at 140 ℃ for 10h to constant weight, and transferring to a dryer to cool to room temperature for later use;
(2) preparation of aqueous phase solution: preparing an aqueous solution containing ethylenediamine and PVA, wherein the concentration of the aqueous solution is respectively 2 wt% of ethylenediamine and 0.07 wt% of PVA, heating to 95 ℃, and stirring for 2 hours; slowly adding 0.03 wt% of carboxylic acid carbon nano tube, dropwise adding sodium hydroxide to adjust the pH value of the aqueous solution to 7, and performing ultrasonic treatment for 1h at room temperature to obtain an aqueous phase solution;
(3) preparation of organic phase solution: dissolving trimesoyl chloride in cyclohexane to form an organic phase solution, wherein the concentration of the trimesoyl chloride is 0.3 wt%, and fully stirring and dissolving to obtain the organic phase solution;
(4) soaking a polysulfone base membrane in an aqueous phase solution for 5min, contacting the aqueous phase solution only on the front surface of the membrane, taking out the soaked membrane, slightly rolling the surface of the membrane for 2 times by using a rubber roller, removing redundant bubbles and the aqueous phase solution on the surface, then contacting the membrane with an organic phase solution for 30s, completing interfacial polymerization reaction, finally drying the membrane in a vacuum oven at 45 ℃ for 10min, completing solidification and shaping of an ultrathin polyamide separation layer, preparing the high-flux reverse osmosis membrane based on the carbon nano tube and PVA, and storing the membrane in deionized water.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for preparing a high flux reverse osmosis membrane, comprising:
providing a base film;
and taking the surface of the basement membrane as an aqueous phase-oil phase interface of an aqueous phase solution containing polyamine monomers, carboxylic acid carbon nano tubes and polyvinyl alcohol and an organic phase solution containing polybasic acyl chloride, and carrying out interfacial polymerization reaction on the polyamine monomers and the polybasic acyl chloride at the interface so as to form an ultrathin polyamide separation layer on the surface of the basement membrane, thereby obtaining the high-flux reverse osmosis membrane.
2. The method according to claim 1, comprising:
fully soaking the surface of the base film for 1-5min by using the aqueous phase solution; and the number of the first and second groups,
and fully infiltrating the surface of the basement membrane with the organic phase solution, so that the polyamine monomer and the polyacyl chloride carry out interfacial polymerization reaction for 10-30s at the interface.
3. The method according to claim 1 or 2, characterized in that it comprises in particular:
mixing polyamine monomer, polyvinyl alcohol and water, stirring for 2-5h at 85-95 ℃, then adding a carboxylated carbon nanotube and an acid absorbent, uniformly mixing to form the aqueous phase solution, and adjusting the pH value of the aqueous phase solution to 7.0-9.0; preferably, the acid absorbent includes any one or a combination of two or more of sodium hydroxide, triethylamine and pyridine.
4. The method of claim 1, wherein: the length of the carboxylated carbon nanotube is 0.5-2 mu m;
and/or the carboxylated carbon nanotube is a one-dimensional hollow tubular nano material rolled by a graphite sheet layer;
and/or the number average molecular weight of the polyvinyl alcohol is 25000-30000 Da;
and/or the polyamine monomer comprises m-phenylenediamine and/or ethylenediamine;
and/or the concentration of polyamine monomer in the aqueous phase solution is 1-5 wt%;
and/or, the concentration of the carboxylated carbon nanotubes in the aqueous phase solution is 0.01 to 0.05 weight percent;
and/or the concentration of polyvinyl alcohol in the aqueous phase solution is 0.05-0.1 wt%.
5. The method according to claim 1, comprising: uniformly mixing polyacyl chloride with an organic solvent to form the organic phase solution; preferably, the organic solvent comprises n-hexane and/or cyclohexane;
and/or, the polybasic acid chloride comprises trimesoyl chloride;
and/or the concentration of the polybasic acyl chloride in the organic phase solution is 0.1-0.5 wt%.
6. The production method according to claim 1, characterized by comprising: immersing the base membrane in the aqueous phase solution for 1-5min, removing the residual aqueous phase solution and redundant bubbles in the base membrane, immersing in the organic phase solution for 10-30s, performing interfacial polymerization to form an ultrathin polyamide separation layer, taking out and drying to obtain the high-flux reverse osmosis membrane.
7. The method of claim 1, further comprising: after the interfacial polymerization reaction is finished, drying the base film with the surface undergoing the interfacial polymerization reaction in an oven at the temperature of 45-75 ℃ for 5-10min, and curing and forming to form the ultrathin polyamide separation layer;
and/or, the base film comprises a polysulfone base film.
8. A high flux reverse osmosis membrane made by the method of any one of claims 1-7.
9. The high flux reverse osmosis membrane of claim 8, wherein: the high-flux reverse osmosis membrane comprises a base membrane and an ultrathin polyamide separation layer which are sequentially stacked, wherein the ultrathin polyamide separation layer is adsorbed on the surface of the base membrane through a physical effect, the carboxylated carbon nanotubes and polyvinyl alcohol are embedded in the ultrathin polyamide separation layer, and the carboxylated carbon nanotubes and the polyvinyl alcohol are combined through hydrogen bonds;
preferably, the thickness of the ultrathin polyamide separation layer is 150-250nm, and the density ranges from 1.1 to 1.2g/cm3；
Preferably, the high-flux reverse osmosis membrane has the water flux of 52.7L/m under the conditions of 15.5bar, 2000ppmNaCl aqueous solution, 25 ℃ and pH value of 7-82h, the salt rejection rate reaches 98.7 percent;
preferably, the contact angle between the high-flux reverse osmosis membrane and water is 0-47 degrees.
10. Use of the high flux reverse osmosis membrane of claim 9 in the field of desalination of sea water, brackish water desalination or sewage treatment.
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