CN-122006482-A - Polyether sulfone hollow fiber membrane component with dual intelligent response and closed-loop control and preparation method thereof

CN122006482ACN 122006482 ACN122006482 ACN 122006482ACN-122006482-A

Abstract

The invention discloses a polyether sulfone hollow fiber membrane component with dual intelligent response and closed-loop control and a preparation method thereof, the component comprises a membrane filament bundle, an intelligent control system, a transparent shell, an end cover and an inlet/outlet interface, wherein the membrane filament bundle consists of a plurality of polyether sulfone hollow fiber membrane filaments, the inner surfaces of the membrane filaments are grafted with temperature response polymers to form an inner surface temperature response layer, the outer surfaces of the membrane filaments are grafted with pH response polymers to form an outer surface pH response layer, an inner and outer partition and function cooperative dual intelligent response layer is formed, an independent anchoring gradient transition layer is arranged between the response layer and a membrane substrate, the polymer density of the gradient transition layer gradually decreases from the membrane surface to the inner direction of the membrane substrate, the gradient transition layer is used for anchoring the response layer on the surface of the substrate, the bonding force is enhanced, the dropping is prevented, the intelligent control system integrates a temperature sensor, a pH sensor, a microprocessor and an electrothermal element to form a closed-loop control circuit, and the membrane performance can be adjusted in real time and self-adaption according to feeding conditions.

Inventors

LIANG YI
ZHANG YANG
SUN CHAO

Assignees

河南净必滢环境科技有限公司

Dates

Publication Date: 20260512
Application Date: 20260326

Claims (10)

1. A polyether sulfone hollow fiber membrane component with dual intelligent response and closed-loop control and a preparation method thereof are provided, wherein the polyether sulfone hollow fiber membrane component comprises a membrane filament bundle, an intelligent control system, a transparent shell, an end cover and an inlet/outlet interface, and is characterized in that the membrane filament bundle is composed of a plurality of polyether sulfone hollow fiber membrane filaments, the inner surface of each polyether sulfone hollow fiber membrane filament is grafted with a temperature response polymer to form an inner surface temperature response layer, the outer surface of each polyether sulfone hollow fiber membrane filament is grafted with a pH response polymer to form an outer surface pH response layer, and thus a dual intelligent response layer with inner and outer surface functional partitions is formed; The intelligent control system comprises a temperature sensor, a pH sensor, a microprocessor and an electric heating element, wherein the temperature sensor and the pH sensor are used for monitoring parameters of feed fluid in real time, a control algorithm is preset in the microprocessor and is used for receiving sensor signals and dynamically adjusting the power of the electric heating element according to target separation performance, and the electric heating element is used for heating membrane tows according to the control instruction so as to form a closed-loop control loop for regulating and controlling the membrane separation performance in real time; the inner wall of the transparent shell is provided with a reflective coating, and the electric heating element is a transparent conductive film or a metal grid attached to the inner wall of the transparent shell.
2. The polyether sulfone hollow fiber membrane assembly with dual intelligent response and closed loop control and the preparation method thereof, as claimed in claim 1, wherein the temperature response polymer is poly N-isopropyl acrylamide or poly N-vinyl caprolactam, the pH response polymer is poly dimethylaminoethyl methacrylate or polyacrylic acid, the thickness of the independent anchoring gradient transition layer is 0.5-2 μm, and the polymer density thereof gradually decreases from the membrane surface to the inner direction of the membrane matrix.
3. The polyether sulfone hollow fiber membrane assembly with dual intelligent response and closed loop control and the preparation method thereof as claimed in claim 1, wherein the control algorithm preset in the microprocessor is a fuzzy control algorithm or a neural network algorithm and is used for dynamically adjusting the power of the electric heating element according to the temperature, the pH signal and the target separation performance.
4. A method of making the dual intelligent response and closed loop control polyethersulfone hollow fiber membrane assembly of any one of claims 1-3 comprising the steps of: S1, preparing a polyether sulfone hollow fiber base membrane; s2, preparing a gradient transition layer and a dual response layer on the surface of the membrane wire in an independent anchoring way; S3, assembling an intelligent control system; S4, integrally assembling the membrane component.
5. The method according to claim 4, wherein in the step S1, a dry-wet spinning method is used for preparing the base film, and in the step S2, an atomic transfer radical polymerization or a reversible addition-fragmentation chain transfer polymerization method is used for modifying the surface of the film yarn.
6. The method according to claim 4, wherein the polyether sulfone hollow fiber base membrane in step S1 is prepared by the following steps: S1.1, taking polyethersulfone as a membrane material, taking one or a mixture of two or more solvents of N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) as solvents, adding a pore-forming agent (such as polyethylene glycol and polyvinylpyrrolidone), stirring and dissolving at 45-95 ℃ to form a casting membrane solution with the mass fraction of 15-25%; S1.2, extruding a casting solution through a spinneret, adopting a dry-wet spinning method, controlling the dry spinning distance to be 0.1-15cm, controlling the coagulation bath temperature to be room temperature-99 ℃, and preparing the polyether sulfone hollow fiber base membrane by taking one or a mixture of more than two solvents of water and N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) as the solvent (the concentration is 5-70 percent), wherein the traction speed is 1-30 m/min; S1.3, soaking the base film in deionized water for 24-48h, removing residual solvent and pore-forming agent, and airing for standby.
7. The method according to claim 4, wherein the preparation of the gradient transition layer and the dual response layer on the surface of the membrane filament in step S2 specifically comprises the following steps: s2.1, carrying out surface modification on the polyether sulfone hollow fiber base membrane by adopting an atom transfer radical polymerization or a reversible addition-fragmentation chain transfer polymerization method; S2.2, performing activation treatment on the basal membrane, namely immersing the basal membrane into a dopamine solution with the concentration of 1-3 mg/mL, adjusting the pH value of the solution to 8.5 by using Tris-HCl buffer solution, and immersing for 12-24 hours at the temperature of 25-35 ℃ to form a polydopamine coating on the surface of the basal membrane; S2.3, preparing an independent anchoring gradient transition layer, namely finishing the activated base film into a bundle, packaging the two ends of the bundle in end covers by using epoxy resin, ensuring tightness, forming a film wire inner core, packaging the film wire inner core in a shell, and sealing the end covers and the shell by using rubber rings. Firstly, slowly circulating a mixed reaction solution containing a temperature-responsive monomer, an initiator and a catalyst on the inner surface of a membrane wire, then slowly circulating a mixed reaction solution containing a pH-responsive monomer, an initiator and a catalyst on the outer surface of the membrane wire, controlling the reaction temperature to be 45-85 ℃ and the reaction time to be 6-12 hours, and copolymerizing a temperature-responsive polymer and a pH-responsive polymer on the surface of the membrane by regulating the concentration and reaction kinetics of the monomers to form an independent anchoring gradient transition layer with the polymer density gradually reduced from the surface to the inside, wherein the thickness is 0.5-2 mu m; S2.4, preparing a dual intelligent response layer, namely supplementing corresponding temperature response monomers and pH response monomers in the reaction system in the step S2.3, selectively grafting the temperature response polymers on the inner surface of the membrane wires to form a temperature response layer, selectively grafting the pH response polymers on the outer surface of the membrane wires to form a pH response layer by controlling reaction conditions, extracting the inner core of the membrane wires after the reaction is finished, cutting off part of the membrane wires encapsulated in epoxy resin, fully flushing the membrane wires with deionized water, removing unreacted monomers and homopolymers, and airing to obtain the dual intelligent response type membrane wires.
8. The method according to claim 4, wherein the intelligent control system of step S3 is assembled as follows: S3.1, embedding a temperature sensor and a pH sensor into the end cover of the membrane assembly to ensure that a probe of the membrane assembly can be fully contacted with feed fluid; S3.2, fixing the microprocessor on the outer side of the end cover, and connecting the microprocessor with the sensor and the electric heating element (transparent conductive film or metal grid) through a wire; S3.3, spraying a reflective coating on the inner wall of the transparent shell, and attaching an electric heating element (transparent conductive film or metal grid) to the inner wall; and S3.4, connecting and debugging all the components to ensure accurate signal transmission of the sensor, effective control logic of the microprocessor and uniform heating of the electric heating element.
9. The method according to claim 4, wherein the overall assembly of the membrane module in step S4 is specifically as follows: s4.1, finishing the prepared double intelligent response type polyether sulfone hollow fiber membrane wires into a bundle, and packaging two ends of the bundle in an end cover by using epoxy resin to ensure tightness; s4.2, sealing and connecting the end cover of the packaged membrane tows with the transparent shell, and installing a water inlet, a water producing port and a water concentrating port; s4.3, electrically and mechanically connecting the assembled intelligent control system with the membrane module main body; s4.4, detecting the air tightness and debugging the performance of the completely assembled membrane assembly, and ensuring that the completely assembled membrane assembly meets the design requirements.
10. The polyether sulfone hollow fiber membrane assembly with double intelligent response and closed loop control and the preparation method thereof, which are disclosed in claim 1, are characterized in that the polyether sulfone hollow fiber membrane wire is provided with an asymmetric spongy pore structure, and comprises a supporting layer, an inner surface layer and an outer surface layer, wherein the inner surface layer and the outer surface layer are covered on the supporting layer, the average pore diameter of the supporting layer is 10-50 times of that of the inner surface layer, the average pore diameter of the inner surface layer is 0.027-0.032 mu m, the inner diameter of the hollow fiber membrane is 450-550 mu m, and the wall thickness is 200-300 mu m.

Description

Polyether sulfone hollow fiber membrane component with dual intelligent response and closed-loop control and preparation method thereof Technical Field The invention relates to the technical field of membrane separation, in particular to a polyether sulfone hollow fiber membrane module with double intelligent response and closed-loop control and a preparation method thereof, and specifically relates to a polyether sulfone hollow fiber membrane module with double intelligent response and closed-loop control and a preparation method thereof. Background The polyethersulfone hollow fiber membrane has wide application in the fields of hemodialysis, industrial water treatment, biological separation and the like due to excellent mechanical strength, thermal stability and chemical tolerance, however, the traditional polyethersulfone membrane has the problems of strong surface hydrophobicity, easiness in pollution by organic matters such as protein and the like, fixed water flux and interception rate performance and the like, and when a material system with complex or dynamic component change is treated, the traditional membrane cannot adaptively adjust the separation performance, so that the efficiency is reduced and the membrane pollution is aggravated. In order to improve the problems, the hydrophilic or functional polymer is generally introduced by blending modification or surface grafting in the prior art, and in recent years, the intelligent response type polymer (such as a temperature-sensitive and pH-sensitive polymer) is grafted on the surface of the membrane, so that the membrane has a certain environment response capability, however, most of researches are focused on a single response mechanism (only temperature or only pH), complex environments with multiple parameter coupling changes in practical application are difficult to deal with, in addition, the existing intelligent response membrane stays at a material level, systematic design integrated with a sensing and executing unit is lacking, real-time, closed-loop and precise regulation of a separation process cannot be realized, and the problems of single response signal, regulation lag, uneven heating of the membrane surface, easy falling of a response layer and the like exist in part of membrane components for attempting integrated control, so that the development of the intelligent membrane separation module which can simultaneously respond to multiple environment signals, has real-time dynamic optimization of performance, is stable and reliable and has become a technical problem to be solved in the field. Disclosure of Invention The invention mainly aims to overcome the defects of the prior art and provides a polyether sulfone hollow fiber membrane component with double intelligent response and closed-loop control and a preparation method thereof. According to the scheme, different types of intelligent response layers are built on the inner surface and the outer surface of the membrane wire in a partitioning mode, an advanced closed-loop control system is integrated, and cooperative and self-adaptive regulation and control of the membrane aperture and the surface charge are achieved, so that the separation efficiency, the selectivity and the pollution resistance of the membrane under dynamic conditions are remarkably improved. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: A polyether sulfone hollow fiber membrane module with dual intelligent response and closed-loop control and a preparation method thereof are provided, wherein the polyether sulfone hollow fiber membrane module comprises a membrane filament bundle, an intelligent control system, a transparent shell, an end cover and an inlet/outlet interface. The membrane filament bundle consists of a plurality of polyether sulfone hollow fiber membrane filaments, and is characterized in that the inner surface of the membrane filaments is grafted with temperature response polymers (such as PNIPAM or PNVCL), the outer surface of the membrane filaments is grafted with pH response polymers (such as PDMAEMA or PAA) to form an inner-outer partition and functional synergistic dual intelligent response layer, an independent anchoring gradient transition layer formed by copolymerization of the temperature response polymers and the pH response polymers, which gradually reduces the polymer density from the membrane surface to the inner direction of the membrane matrix, is arranged between the response layer and the membrane matrix, is used for anchoring the response layer on the matrix surface, enhancing the binding force and preventing falling, the intelligent control system integrates a temperature sensor, a pH sensor, a microprocessor and an electric heating element to form a closed loop control circuit, the working state of the membrane can be regulated in real time according to feeding conditions, a control algorithm is preset in the microprocessor an