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CN-121988186-A - High-temperature-resistant reverse osmosis membrane prepared based on acyl chloride graphene oxide and ultrasonic assistance and preparation method thereof

CN121988186ACN 121988186 ACN121988186 ACN 121988186ACN-121988186-A

Abstract

The invention relates to the technical field of reverse osmosis composite membranes, in particular to a high-temperature-resistant reverse osmosis membrane prepared based on acyl chloride graphene oxide and ultrasonic assistance and a preparation method thereof. According to the invention, acyl chloride and graphene oxide react to synthesize acyl chloride graphene oxide (GO-COCl), isoparaffin solvent Isopar G is used as a dispersing agent to be added into an organic phase, meanwhile, ultrasonic auxiliary treatment is carried out on the organic phase solution before interfacial polymerization, so that GO-COCl is uniformly dispersed in the organic phase, and finally, the composite reverse osmosis membrane is prepared through interfacial polymerization of m-phenylenediamine (MPD) and 1,3, 5-trimesic acid chloride (TMC). According to the method, the GO-COCl can be added into the PA layer instead of the surface or the substrate through crosslinking, the acid chloride in the GO-COCl reacts with the amine monomer to form a polyamide chain, and meanwhile, the organic phase solution is subjected to ultrasonic dispersion before interfacial polymerization, so that the uniform GO-COCl sheet is clamped in the PA layer, and the flux, the desalination performance and the stability of the composite reverse osmosis membrane are improved.

Inventors

  • XU HAOYANG
  • ZHAO LIANRUI
  • KANG YAN
  • WU ZONGCE

Assignees

  • 沃顿科技股份有限公司

Dates

Publication Date
20260508
Application Date
20241105

Claims (10)

  1. 1. The preparation method of the high-temperature-resistant reverse osmosis membrane based on the acyl chloride graphene oxide and the ultrasonic auxiliary preparation is characterized by comprising the following steps: (1) Preparation of a base film: Mixing Polysulfone (PSF) powder and N, N-Dimethylformamide (DMF) solvent, stirring uniformly until polysulfone is dissolved in N, N-dimethylformamide and transparent membrane liquid is formed; (2) Preparation of GO-COCl: Firstly, respectively dissolving Triethylamine (TEA) and bis (trichloromethyl) carbonate (BTC) in carbon tetrachloride (CCl 4 ) to obtain TEA-CCl 4 and BTC-CCl 4 , ultrasonically dispersing Graphene Oxide (GO) in isoparaffin solvent Isopar G, then adding the GO-Isopar G solution into BTC-CCl 4 in nitrogen atmosphere, continuously stirring and dropwise adding the TEA-CCl 4 solution into a mixed system until the solution is uniform and stable, finally, refluxing the mixed solution for 5-10 hours at 60-80 ℃ and then vacuum filtering, and washing to remove byproducts by using Isopar G to obtain GO-COCl; (3) Polyamide skin layer construction: Dissolving m-phenylenediamine (MPD) in deionized water to serve as a water phase, dissolving 1,3, 5-trimellitic chloride (TMC) in normal hexane to serve as an oil phase, respectively placing the water phase and the oil phase in two containers to substitute, dispersing the GO-COCl prepared in the step (2) in Isopar G, adding the Isopar G into the oil phase solution, carrying out constant-temperature ultrasonic dispersion treatment, immersing non-woven fabric with polysulfone base membrane in the water phase solution, removing superfluous liquid on the surface, immersing the base membrane in the container filled with the oil phase, and drying the prepared membrane and preserving the membrane at low temperature.
  2. 2. The method according to claim 1, wherein the ratio of the polysulfone powder to N, N-dimethylformamide is in the range of mass ratio (7:93) - (21:79).
  3. 3. The method according to claim 2, wherein the ratio of the polysulfone powder to N, N-dimethylformamide is 13:87 by mass.
  4. 4. The method according to claim 1, wherein a transparent film liquid is formed in the step (1).
  5. 5. The process according to claim 1, wherein the TEA-CCl4 is present in a concentration of 0.05-0.45g/mL.
  6. 6. The method according to claim 1, wherein the concentration of BTC-CCl4 is 0.5 to 1g/mL.
  7. 7. The method according to claim 1, wherein in the step (3), m-phenylenediamine (MPD) is dissolved in deionized water as an aqueous phase at a concentration of 2 to 5wt%.
  8. 8. The preparation method according to claim 1, wherein 0.1-0.6wt% of 1,3, 5-trimesic acid chloride (TMC) is dissolved in n-hexane as an oil phase, and the GO-COCl prepared in the above (2) is dispersed in Isopar G at a ratio of 0.15w/v% and then added to the oil phase solution at a ratio of 0.002 wt%.
  9. 9. The method according to claim 1, characterized in that the constant temperature ultrasonic dispersion treatment, in particular power 300W, frequency 40kHz, ultrasonic for 20-30 minutes.
  10. 10. A high temperature resistant reverse osmosis membrane based on acid chloride graphene oxide and ultrasound-assisted preparation prepared by the preparation method of any one of claims 1-8.

Description

High-temperature-resistant reverse osmosis membrane prepared based on acyl chloride graphene oxide and ultrasonic assistance and preparation method thereof Technical Field The invention relates to the technical field of reverse osmosis composite membranes, in particular to a high-temperature-resistant reverse osmosis membrane prepared based on acyl chloride graphene oxide and ultrasonic assistance and a preparation method thereof. Background In recent years, a pressure-driven seawater desalination membrane using a reverse osmosis technology has become a leading-edge technology for producing fresh water from brine. However, the widespread use of this technology still faces some challenges. In order to ensure the long-term use of the membrane element, the temperature of a water sample to be treated is usually controlled below 45 ℃, and high-temperature wastewater (60-95 ℃) in the industries of papermaking, textiles and the like is required to be cooled to an allowable temperature before being treated, so that the membrane element is subjected to membrane separation, and the development of a reverse osmosis membrane which is high-temperature resistant and has excellent comprehensive performance is of great significance. One new concept for preparing advanced reverse osmosis membranes is to integrate nanoparticles into a Polyamide (PA) layer to create a composite structure, and various types of hydrophilic porous and non-porous nanomaterials have been used to modify reverse osmosis membranes such as nano-silver, titania, silica, carbon nanotubes, and the like. Therefore, finding a high-temperature-resistant reverse osmosis membrane with excellent high-temperature resistance and long-term stability is still an important research direction at present. Graphene Oxide (GO) retains the advantages of graphene structure, with increased oxygen-containing functional groups thereon, making the properties more reactive than graphene. In the process of preparing the PA layer, a certain amount of GO is embedded in the interfacial polymerization, so that the water flux, stability, anti-fouling performance and chlorine resistance of the membrane can be effectively improved, and meanwhile, the loss of the desalination performance of the membrane is almost negligible, so that the PA layer is an ideal modification additive. Although the addition of GO to the aqueous phase is easy to achieve, the rubber roll will peel off some of the GO from the film surface when too much of the aqueous phase is removed prior to interfacial polymerization, and the lamellar structure will be destroyed. In contrast, when dispersed in an organic phase, GO can be distributed layer by layer from the organic phase on a support layer, but GO is difficult to uniformly disperse in the organic phase. Disclosure of Invention In order to solve the technical problems in the prior art, the invention provides a high-temperature-resistant reverse osmosis membrane prepared based on acyl chloride graphene oxide and ultrasonic assistance and a preparation method thereof. A preparation method of a high-temperature-resistant reverse osmosis membrane based on acyl chloride graphene oxide and ultrasonic auxiliary preparation comprises the following steps: (1) Preparation of a base film: Mixing Polysulfone (PSF) powder and N, N-Dimethylformamide (DMF) solvent, stirring uniformly until polysulfone is dissolved in N, N-dimethylformamide and transparent membrane liquid is formed; (2) Preparation of GO-COCl: Firstly, respectively dissolving Triethylamine (TEA) and bis (trichloromethyl) carbonate (BTC) in carbon tetrachloride (CCl 4) to obtain TEA-CCl4 and BTC-CCl4, ultrasonically dispersing Graphene Oxide (GO) in isoparaffin solvent Isopar G, then adding the GO-Isopar G solution into the BTC-CCl4 in a nitrogen atmosphere, continuously stirring and dropwise adding the TEA-CCl4 solution into a mixed system until the solution is uniform and stable, finally, refluxing the mixed solution for 5-10 hours at 60-80 ℃ and then vacuum filtering, and washing to remove byproducts by the Isopar G to obtain GO-COCl; (3) Polyamide skin layer construction: Dissolving m-phenylenediamine (MPD) in deionized water to serve as a water phase, dissolving 1,3, 5-trimellitic chloride (TMC) in normal hexane to serve as an oil phase, respectively placing the water phase and the oil phase in two containers to substitute, dispersing the GO-COCl prepared in the step (2) in Isopar G, adding the Isopar G into the oil phase solution, carrying out constant-temperature ultrasonic dispersion treatment, immersing non-woven fabric with polysulfone base membrane in the water phase solution, removing superfluous liquid on the surface, immersing the base membrane in the container filled with the oil phase, and drying the prepared membrane and preserving the membrane at low temperature. Further, the ratio of the polysulfone powder to N, N-dimethylformamide is in the mass ratio (7:93) - (21:79). Preferably, the ratio