CN110743383B - Modification method for improving permeation flux of polyamide composite membrane - Google Patents
Modification method for improving permeation flux of polyamide composite membrane Download PDFInfo
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- CN110743383B CN110743383B CN201911002970.4A CN201911002970A CN110743383B CN 110743383 B CN110743383 B CN 110743383B CN 201911002970 A CN201911002970 A CN 201911002970A CN 110743383 B CN110743383 B CN 110743383B
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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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D69/02—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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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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
- 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 relates to a modification method for improving permeation flux of a polyamide composite membrane, which successfully introduces amphoteric molecules into the surface and the pore wall of the polyamide composite membrane by using 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and sultone, and improves the separation performance of the composite membrane by using stronger hydrophilicity of the amphoteric molecules. The invention has the advantages that: (1) The modification method is simple to operate, no specific monomer is required to be synthesized, and the interception performance of the original composite membrane is not sacrificed; (2) The method has wide application range and easy scale production, and can effectively improve the permeation flux of polyamide composite reverse osmosis, forward osmosis, nanofiltration membranes and the like.
Description
Technical Field
The invention relates to a modification method for improving the permeation flux of a polyamide composite membrane, belonging to the technical field of separation membrane preparation.
Background
As a new separation technology, the membrane filtration technology has the advantages of high efficiency, low energy consumption, easy operation and the like, can realize the recycling of wastewater and the resource recovery of useful substances, is widely used in the fields of drinking water purification, wastewater treatment, biopharmaceuticals, petrochemical industry and the like, and currently used membrane materials mainly comprise cellulose acetate, aromatic polyamides, sulfonated polysulfones and the like. The polyamide composite membrane is prepared from polyamine and polyacyl chloride through interfacial polymerization, has excellent water permeability and selective separation performance, and occupies a dominant position in the fields of reverse osmosis, forward osmosis and nanofiltration membrane production and application all over the world.
Although the polyamide composite membrane is widely welcomed in industrial production as a polymer membrane material with great application prospect, the current commercialized polyamide composite membranes are difficult to break through the balance effect between permeability and selectivity. On the premise of ensuring high retention rate, how to further improve permeation flux has become a key point and a difficult point in the current research. The realization method of the high-flux polyamide composite membrane mainly comprises the steps of increasing the surface hydrophilicity of the membrane, introducing a porous nano material into a separation layer, reducing the thickness of the separation layer and the like.
The most common technology is that hydrophilic macromolecules such as chitosan, polyvinyl alcohol, polyethylene glycol and the like are introduced into the surface of the polyamide composite membrane by means of coating, crosslinking, chemical grafting and the like, and the affinity between the surface of the membrane and water molecules is increased to improve the permeation flux. However, the method has high requirements on the deposition amount control of hydrophilic macromolecules, and once excessive, the mass transfer resistance of water molecules is increased rapidly, and the permeation flux of the polyamide composite membrane is reduced.
With the rapid development of nanomaterials in recent years, more researchers introduce inorganic nanoparticles into a polyamide separation layer to improve the mass transfer efficiency of water molecules. For example, livingston et al doped with MOF nanoparticles in a polyamide separation layer, the results show that the membrane permeation flux is increased by more than several times on the premise of ensuring small decrease of the salt rejection rate of the membrane. They believe that this is because the pore size in the MOF nanoparticles is larger than water molecules but smaller than inorganic salt ions, and therefore can provide additional permeation channels for water molecules with the entrapment of inorganic salt ions. Certainly, for example, rajaeian and the like think that the nanoparticles are introduced mainly because interface gaps and even defects formed between the nanoparticles and a polymer matrix provide additional channels for water molecules, after all, under the condition of improving the mass transfer rate of the water molecules, the retention rate of inorganic salts still slightly decreases, which shows that the mass transfer rate of inorganic salt ions is also increased and the increased rate is larger than that of the water molecules, namely, the introduction of the nanoparticles is likely to form nonselective mass transfer defects, which is also the reason that the organic-inorganic mixed matrix thin-layer composite membrane is widely researched in the academic field but is not widely applied in industrial production.
In addition, with the continuous and deep research of the interfacial polymerization mechanism, the research has been carried out to construct an ultrathin polyamide separation layer by adjusting the surface physicochemical property and microstructure of the polysulfone base film, so as to realize the improvement of the separation performance of the composite film. For example, livingston and the like construct a cadmium hydroxide nanowire sacrificial layer on a polyimide support membrane through a suction filtration method, realize the uniform distribution of aqueous phase solution on the surface of a base membrane, and control the diffusion rate of aqueous phase monomers to an organic phase, thereby obtaining a polyamide separation layer with the thickness of less than 10nm and greatly improving the permeation flux of the polyamide composite membrane. On the basis, xu et al construct a hydrophilic intermediate transition layer on the surface of a base membrane by a bionic dopamine/polyphenol auxiliary codeposition technology, thereby not only regulating and controlling the interfacial polymerization process and improving the separation performance of the composite membrane, but also effectively utilizing the high adhesion capability of dopamine to improve the interfacial bonding between a polyamide separation layer and the base membrane. However, in the actual use process, the polyamide composite membrane is easily polluted by organic matters in the feeding liquid, periodic chemical cleaning is needed, and if the thickness of the polyamide separation layer is too thin, defects are easily caused to reduce the interception performance, so that the water quality of produced water is not satisfactory.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modification method for improving the permeation flux of a polyamide composite membrane, which can effectively improve the permeation flux of polyamide composite reverse osmosis, forward osmosis, nanofiltration membranes and the like.
According to the invention, the polyamide composite membrane is sequentially treated by using 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and sultone, namely, the amphiphilic micromolecules can be introduced on the surface and the pore wall of the polyamide composite membrane in a chemical bond mode, so that a water molecule layer is formed by using the strong action of the amphiphilic micromolecules and water molecules, the mass transfer rate of the water molecules in the polyamide layer is accelerated, and the purpose of improving the permeation flux of the polyamide composite membrane is finally realized.
The invention provides a modification method for improving the permeation flux of a polyamide composite membrane.
The invention provides a modification method for improving permeation flux of a polyamide composite membrane, wherein the sultone sulfonate is one or more of 1, 4-butyl sultone, 1, 3-propane sultone, 1, 8-naphthalene sultone and the like.
The invention provides a modification method for improving the permeation flux of a polyamide composite membrane, wherein the mass concentration of a 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution is 0.01-2.0%.
The invention provides a modification method for improving the permeation flux of a polyamide composite membrane, wherein the pH value of a 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution is 3.5-4.5.
The invention provides a modification method for improving permeation flux of a polyamide composite membrane, wherein the mass concentration of a sultone solution is 5-20%.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the polyamide composite membrane is sequentially treated by using 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and sultone solution, so that amphiphilic molecules can be introduced into the surface or the wall of the membrane, and the chemical potential of water molecules on the surface of the membrane and the wall of the hole is improved and the mass transfer of the water molecules is accelerated by utilizing the extremely strong acting force between the amphiphilic molecules and the water molecules, thereby realizing the purpose of improving the separation performance of the membrane. The method is simple to operate, does not need to synthesize specific monomers, and does not influence the interception performance of the original composite membrane; and the application range is wide, and the modification can be performed on commercial polyamide composite reverse osmosis, forward osmosis, nanofiltration membranes and the like.
Detailed Description
The following is a detailed description of the practice of the invention;
comparative example 1:
washing a commercial polyamide composite nanofiltration membrane with pure water, soaking in a hydrochloric acid aqueous solution with the pH =4.0 for 4 hours, taking out, and washing with pure water; then, the mixture was immersed in an ethanol/water (mass ratio 1.
The desalination rate and water flux of the nanofiltration membrane were measured at a NaCl concentration of 500mg/l, a pressure of 0.5MPa, a temperature of 25 ℃ and a pH of 7.0-8.0, and the results are shown in Table 1.
Example 1:
washing a commercial polyamide composite nanofiltration membrane with pure water, soaking in an aqueous solution (pH = 4.0) containing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride at a mass concentration of 0.5% for 4 hours, taking out, and washing with pure water; then, the mixture was immersed in an ethanol/water (mass ratio 1.
The desalination rate and water flux of the nanofiltration membrane were measured at a NaCl concentration of 500mg/l, a pressure of 0.5MPa, a temperature of 25 ℃ and a pH of 7.0-8.0, and the results are shown in Table 1.
Example 2:
washing a commercial polyamide composite nanofiltration membrane with pure water, soaking the membrane in an aqueous solution (pH = 4.0) with the mass concentration of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride being 0.5% for 4 hours, taking out the membrane, and washing the membrane with pure water; then, the mixture was immersed in an ethanol/water (mass ratio 1.
The desalination rate and water flux of the nanofiltration membrane were measured at a NaCl concentration of 500mg/l, a pressure of 0.5MPa, a temperature of 25 ℃ and a pH of 7.0 to 8.0, and the results are shown in Table 1.
Example 3:
washing a commercial polyamide composite nanofiltration membrane with pure water, soaking in an aqueous solution (pH = 4.0) containing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride at a mass concentration of 0.5% for 4 hours, taking out, and washing with pure water; then, the mixture was immersed in an ethanol/water (mass ratio 1.
The desalination rate and water flux of the nanofiltration membrane were measured at a NaCl concentration of 500mg/l, a pressure of 0.5MPa, a temperature of 25 ℃ and a pH of 7.0 to 8.0, and the results are shown in Table 1.
Comparative example 2:
washing a commercial polyamide composite reverse osmosis membrane with pure water, soaking in a hydrochloric acid aqueous solution with the pH =4.0 for 4 hours, taking out, and washing with pure water; then, the mixture was immersed in an ethanol/water (mass ratio 1.
The salt rejection and water flux of the reverse osmosis membrane were measured under conditions of NaCl concentration of 1500mg/l, pressure of 1.5MPa, temperature of 25 ℃ and pH of 7.0 to 8.0, and the results are shown in Table 1.
Example 4:
washing a commercial polyamide composite reverse osmosis membrane with pure water, soaking the membrane in an aqueous solution (pH = 4.0) containing 0.5% by mass of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride for 4 hours, taking out the membrane, and washing the membrane with pure water; then, the mixture was immersed in an ethanol/water (mass ratio 1.
The salt rejection and water flux of the reverse osmosis membrane were measured under conditions of a NaCl concentration of 1500mg/l, a pressure of 1.5MPa, a temperature of 25 ℃ and a pH value of 7.0 to 8.0, and the results are shown in Table 1.
TABLE 1 separation Performance of Polyamide composite membranes
The data in the table 1 show that the commercial polyamide composite nanofiltration membrane treated by the method can improve the permeation flux by 35-50% on the basis of keeping the NaCl removal rate unchanged or even slightly increasing; the polyamide composite reverse osmosis membrane is treated, and the permeation flux can also be from 40.6l/m 2 h is increased to 55.4l/m 2 And h, the permeation flux of the polyamide composite membrane can be effectively improved, and a foundation is laid for further reducing the use cost of the membrane separation technology and expanding the application field.
Claims (4)
1. A modification method for improving permeation flux of a polyamide composite membrane is characterized by comprising the following steps: the method comprises the following steps of sequentially treating a polyamide composite membrane by using 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and sultone solution, and introducing amphoteric molecules on the surfaces of the membrane and the pore wall, so as to improve the membrane separation performance:
(1) Cleaning a commercialized polyamide composite membrane with pure water, soaking the polyamide composite membrane in 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution for 4 hours, taking out the polyamide composite membrane, and cleaning the polyamide composite membrane with pure water; the mass concentration of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution is 0.01-2.0%;
(2) And (2) soaking the membrane treated in the step (1) into an ethanol-water solution of sultone, wherein the mass ratio of ethanol to water in the solution is 1: taking out after 1,15 hours, and cleaning with pure water for later use; the sultone sulfonate is one or more of 1, 4-butane sultone, 1, 3-propane sultone or 1, 8-naphthalene sultone.
2. The modification method for improving the permeation flux of the polyamide composite membrane according to claim 1, characterized in that: the polyamide composite membrane is a polyamide composite reverse osmosis membrane, a polyamide composite nanofiltration membrane or a polyamide composite forward osmosis membrane.
3. The modification method for improving the permeation flux of the polyamide composite membrane according to claim 1, characterized in that: the pH value of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution is 3.5-4.5.
4. The modification method for improving the permeation flux of the polyamide composite membrane according to claim 1, characterized in that: the mass concentration of the sultone in the ethanol-water solution of the sultone is 5 to 20 percent.
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| CN115090124B (en) * | 2022-07-01 | 2023-09-05 | 浙江理工大学 | Preparation method and application of electric double layer composite membrane generated by interfacial polymerization reaction |
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| US4960517A (en) * | 1989-12-13 | 1990-10-02 | Filmtec Corporation | Treatment of composite polyamide membranes via substitution with amine reactive reagents |
| CN102824855A (en) * | 2011-06-17 | 2012-12-19 | 中国科学院大连化学物理研究所 | Surface modification method of polyamide reverse-osmosis composite membrane |
| CN103127847B (en) * | 2013-03-15 | 2015-04-15 | 北京化工大学 | Anti-protein-pollution polyacrylonitrile hydrolyzed modified ultra-filtration membrane and preparation method thereof |
| CN103272498B (en) * | 2013-05-14 | 2015-01-21 | 天津大学 | Surface grafting modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
| CN105214521B (en) * | 2014-06-25 | 2017-08-04 | 天津大学 | A kind of polyetherimide amine composite nanofiltration membrane and preparation method |
| US10556222B2 (en) * | 2015-03-10 | 2020-02-11 | The Research Foundation For The State University Of New York | Nanofibrous materials for heavy metal adsorption |
| CN106345323A (en) * | 2016-10-17 | 2017-01-25 | 东华大学 | Preparation method for anti-pollution hydrophilic positive permeable membrane |
| CN109351191A (en) * | 2018-11-21 | 2019-02-19 | 浙江理工大学 | A kind of high-performance reverse osmosis composite membrane and preparation method thereof |
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| CN110180411A (en) * | 2019-05-20 | 2019-08-30 | 浙江工业大学 | A kind of high-flux nanofiltration membrane being modified by sultones and preparation method |
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