CN112403288B - High-strength pollution-resistant composite reverse osmosis membrane and preparation method thereof - Google Patents
High-strength pollution-resistant composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN112403288B CN112403288B CN202011458216.4A CN202011458216A CN112403288B CN 112403288 B CN112403288 B CN 112403288B CN 202011458216 A CN202011458216 A CN 202011458216A CN 112403288 B CN112403288 B CN 112403288B
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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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention relates to a preparation method and application of a high-strength and pollution-resistant composite reverse osmosis membrane, which is characterized in that an aminated carbon nanowire is synthesized and fixed in the reverse osmosis membrane, and a double cross-linked layer of m-phenylenediamine (MPD) -trimesoyl chloride (TMC) and an aminated carbon nanowire-trimesoyl chloride (TMC) is formed by utilizing the high strength of the aminated carbon nanowire and the reactivity of amino, so that the stability and the mechanical strength of a desalting layer are greatly increased, and meanwhile, the excellent dispersing performance, rich hydrophilic amino groups and larger specific surface area of the aminated carbon nanowire also improve the flux and the desalting performance of the reverse osmosis. The test result also shows that the reverse osmosis membrane prepared by the invention has higher mechanical strength, flux and desalination performance compared with the existing reverse osmosis membrane.
Description
Technical Field
The invention relates to the technical field of reverse osmosis membranes, in particular to a preparation method and application of a high-strength pollution-resistant composite reverse osmosis membrane.
Background
Along with the progress of society, the attention degree of people to water resources is gradually improved, and the reverse osmosis membrane is one of the most widely applied and best applied separation membrane products in the separation membrane field.
The interfacial polymerization method is the most dominant method for preparing reverse osmosis composite membranes at present. The polysulfone support layer is used as a basal membrane, and a compact polyamide desalination layer is formed on the polysulfone support layer through the mutual reaction between two active monomers, namely polybasic acyl chloride and polybasic amide. Although reverse osmosis membranes are widely used, the existing reverse osmosis membranes have low strength of a desalting layer caused by the structure of the reverse osmosis membrane, are easy to strip, and have harsh use conditions, and the reduction of the service life is still a big problem, so that the modification of the reverse osmosis membrane to improve the performance of the reverse osmosis membrane is also a main direction of research.
The carbon nano material has become a main development direction of the reverse osmosis composite membrane by adding the carbon nano material in interfacial polymerization because of the high strength, high stability and high specific surface area of the carbon nano material.
CN109876674A discloses a method for modifying the performance of a reverse osmosis membrane by adding acidified carbon nanotubes into an aqueous solution and coating dopamine and silver on the surface of the reverse osmosis membrane, wherein although the strength and flux of the membrane are improved by adding carbon nanotubes, the acidified carbon nanotubes and the dopamine and silver coated subsequently do not interact with each other, and the dispersion of the carbon nanotubes is deteriorated with the subsequent use and the coating layer falls off, which results in the deterioration of the membrane performance.
CN106268379B has applied for one kind and has coated modified acyl chlorination oxidation graphite alkene on reverse osmosis membrane surface, has improved reverse osmosis membrane's flux and antibacterial property, but the problem of droing of graphite alkene layer also is one of follow-up service problems, and when graphite alkene layer drops gradually, reverse osmosis membrane's flux and antibacterial property worsen.
As a new member of the Carbon nanomaterial family, Carbon nanowires (Carbon nanowires) are a new one-dimensional hybrid Carbon nanomaterial with linear Carbon chains wrapped inside Carbon nanotubes: compared with other carbon nano materials, the carbon nano wire has higher purity due to the linear carbon chain and chemical bond formed by the self structure, and has more advantages in the aspects of mechanical strength and functional modification. The application of the carbon nano-wire in the reverse osmosis membrane manufacturing field is not found at present.
Disclosure of Invention
The invention provides a preparation method of a novel aminated carbon nanowire modified high-strength and pollution-resistant composite reverse osmosis membrane. According to the invention, when the crosslinked aromatic polyamide ultrathin desalting layer is prepared by interfacial polymerization, the aminated carbon nanowire is added, and the nanowire is fixed in the reverse osmosis membrane to form a m-phenylenediamine (MPD) -trimesoyl chloride (TMC) and aminated carbon nanowire-trimesoyl chloride (TMC) double crosslinking layer, so that the uniformity and mechanical strength of the desalting layer are greatly increased, and meanwhile, the aminated carbon nanowire has excellent dispersing performance, abundant hydrophilic amino groups and larger specific surface area, and the flux and desalting performance of reverse osmosis are also improved. The service stability is increased, and the service life of the membrane is prolonged.
A high-strength pollution-resistant composite reverse osmosis membrane and a preparation method thereof comprise the following steps:
(1) adding carbon nanowires into a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, heating and ultrasonically treating the mixed solution at 60 ℃ for 4 hours, repeatedly cleaning the mixed solution with deionized water, centrifuging the washed solution until the pH value is 7, and drying the washed solution at 70 ℃ to obtain acidified carbon nanowires;
(2) preparing amino carbon nanowires by loading grafted amino groups on the acidified carbon nanowires through a chemical reaction;
the synthesis method of the amino carbon nano-wire is one of in-situ polymerization, surface initiated grafting, polycondensation reaction, surface curing and electrophilic addition;
the agent used for loading grafted amino in the amino carbon nanowire is one or more of silane coupling agent KH550, triethylamine and polyetherimide;
(3) soaking a polysulfone ultrafiltration membrane (PSF) cleaned by isopropanol in an aqueous phase solution with the pH value of 8 for 30s, removing redundant solution by a rubber roller, soaking in an oil phase solution for 60s, taking out, and performing heat treatment at 70 ℃ for 10min to obtain a high-strength composite reverse osmosis membrane;
the aqueous phase solution comprises the following components in percentage by mass; 0.5-2 wt% of amino carbon nano wire, 2.5 wt% of m-phenylenediamine, 0.2 wt% of triethylamine and 0.3 wt% of camphorsulfonic acid;
the oil phase solution comprises the following raw material components in percentage by mass; 0.07 wt% trimesoyl chloride in n-hexane;
compared with the prior art, the invention has the beneficial effects that:
(1) the amino carbon nano-wire has a linear carbon chain structure, forms more chemical bonds, has higher mechanical strength and stability compared with other carbon nano-materials, can be uniformly distributed in a polyamide layer, and the prepared reverse osmosis membrane has uniform porosity distribution.
(2) In the reverse osmosis membrane prepared by the invention, a m-phenylenediamine (MPD) -trimesoyl chloride (TMC) and an aminated carbon nanowire-trimesoyl chloride (TMC) double cross-linked layer is formed in interfacial polymerization, and the double cross-linked layer can more effectively regulate and control the hydrophilic property, the mechanical strength and the stability of the reverse osmosis membrane and greatly prolong the service life.
Drawings
Fig. 1 is a TEM structure diagram of aminated carbon nanowires.
FIG. 2 is a structural view of a high-strength and contamination-resistant composite reverse osmosis membrane desalination layer prepared by the present invention;
wherein a is an aqueous phase layer, b is an aminated carbon nanowire layer, and c is an oil phase layer.
Detailed Description
The following provides a specific embodiment of a high strength composite reverse osmosis membrane of the present invention.
Example 1
Adding the carbon nano-wire into a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, heating and ultrasonically treating the mixture at 60 ℃ for 4 hours, repeatedly washing the mixture with deionized water, centrifuging the mixture until the pH value is 7, and drying the mixture at 70 ℃ to obtain the acidified carbon nano-wire.
Soaking a polysulfone ultrafiltration membrane (PSF) cleaned by isopropanol in an aqueous phase solution with the pH value of 8 for 30s, wherein the polyether imide modified carbon nanowire (0.5 wt%), m-phenylenediamine (2.5 wt%), triethylamine (0.2 wt%) and camphorsulfonic acid (0.3 wt%) is soaked in an oil phase solution for 60s after removing redundant solution through a rubber roller, wherein trimesoyl chloride (0.07 wt%) and a solvent are n-hexane, and taking out the mixture and carrying out heat treatment at 70 ℃ for 10min to obtain the high-strength composite reverse osmosis membrane;
example 2
The same conditions as in example 1 were applied except that the content of the carbon nanowire was changed to 1 wt%, to obtain a high-strength composite reverse osmosis membrane.
Example 3
The same conditions as in example 1 were applied except that the content of the carbon nanowire was changed to 2 wt%, to obtain a high-strength composite reverse osmosis membrane.
Example 4
The conditions were the same as in example 1 except that KH550 modified carbon nanowires were used, to obtain a high-strength composite reverse osmosis membrane.
Example 5
The conditions were the same as in example 1 except that triethylamine was used to modify the carbon nanowires, to obtain a high-strength composite reverse osmosis membrane.
Comparative example 1
Soaking a polysulfone ultrafiltration membrane (PSF) cleaned by isopropanol in an aqueous phase solution with the pH value of 8 for 30s, wherein m-phenylenediamine (2.5 wt%), triethylamine (0.2 wt%) and camphorsulfonic acid (0.3 wt%) are soaked in an oil phase solution for 60s after removing excessive solution through a rubber roller, wherein trimesoyl chloride (0.07 wt%) and a solvent are n-hexane, taking out, and carrying out heat treatment at 70 ℃ for 10min to obtain the composite reverse osmosis membrane;
comparative example 2
Adding the carbon nano-wire into a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, heating and ultrasonically treating the mixture at 60 ℃ for 4 hours, repeatedly washing the mixture with deionized water, centrifuging the mixture until the pH value is 7, and drying the mixture at 70 ℃ to obtain the acidified carbon nano-wire.
Soaking a polysulfone ultrafiltration membrane (PSF) cleaned by isopropanol in an aqueous phase solution with the pH value of 8 for 30s, wherein acidified carbon nanowires (0.5 wt%), m-phenylenediamine (2.5 wt%), triethylamine (0.2 wt%) and camphorsulfonic acid (0.3 wt%) are soaked in an oil phase solution for 60s after redundant solution is removed by a rubber roller, wherein trimesoyl chloride (0.07 wt%) and a solvent are n-hexane, and taking out the solution and carrying out heat treatment at 70 ℃ for 10min to obtain the composite reverse osmosis membrane;
the film performance test and characterization in the examples and the comparative examples are carried out according to GB/T32373-2015; the test conditions adopted by the invention are that the pH value is 7-8, the concentration of NaCl aqueous solution is 2000ppm, the pressure is 1.55mpa, and the temperature is 25 ℃.
TABLE 1 flux, salt rejection and mechanical Properties of the reverse osmosis membranes of examples and comparative examples
As can be seen from table 1: the high-strength pollution-resistant composite reverse osmosis membrane prepared by the method has excellent flux and desalting performance, and the desalting layer has good stability and high mechanical strength due to the formation of the double cross-linked layer.
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited thereto, and that various modifications and enhancements which fall within the spirit and scope of the invention are possible.
Claims (3)
1. A preparation method of a high-strength pollution-resistant composite reverse osmosis membrane is characterized by comprising the following steps:
(1) adding carbon nanowires into a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, heating and ultrasonically treating the mixed solution at 60 ℃ for 4 hours, repeatedly cleaning the mixed solution with deionized water, centrifuging the washed solution until the pH value is 7, and drying the washed solution at 70 ℃ to obtain acidified carbon nanowires;
(2) preparing amino carbon nanowires by loading grafted amino groups on the acidified carbon nanowires through a chemical reaction;
(3) soaking a polysulfone ultrafiltration membrane cleaned by isopropanol in an aqueous phase solution with the pH value of 8 for 30s, removing redundant solution by a rubber roller, soaking in an oil phase solution for 60s, taking out, and carrying out heat treatment at 70 ℃ for 10min to obtain a high-strength pollution-resistant composite reverse osmosis membrane;
the aqueous phase solution comprises; 0.5-2 wt% of amino carbon nano wire, 2.5 wt% of m-phenylenediamine, 0.2 wt% of triethylamine and 0.3 wt% of camphorsulfonic acid;
the oil phase solution is 0.07 wt% of trimesoyl chloride normal hexane solution;
the reverse osmosis membrane is added with an aminated carbon nanowire while preparing a crosslinked aromatic polyamide ultrathin desalting layer by interfacial polymerization to form a m-phenylenediamine-trimesoyl chloride and aminated carbon nanowire-trimesoyl chloride double crosslinking layer.
2. The method of claim 1, wherein: the synthesis method of the amino carbon nanowire in the step (2) is one of in-situ polymerization, surface-initiated grafting, polycondensation reaction, surface curing and electrophilic addition.
3. The method of claim 1, wherein: in the step (2), the reagent used for loading the grafted amino group in the amino carbon nanowire is one or more of a silane coupling agent KH550, triethylamine and polyetherimide.
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| CN103386258A (en) * | 2013-06-29 | 2013-11-13 | 浙江工业大学 | Preparation method of polyamide composite nanofiltration membrane containing modified carbon nano tube |
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