CN114210210A - Efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction and preparation method thereof - Google Patents
Efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 114
- 239000002121 nanofiber Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000000409 membrane extraction Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002033 PVDF binder Substances 0.000 claims abstract description 56
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 56
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 38
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 38
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 35
- 238000005516 engineering process Methods 0.000 claims abstract description 13
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- 238000012986 modification Methods 0.000 claims abstract description 11
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- 239000000463 material Substances 0.000 claims abstract description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract 12
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract 12
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims abstract 12
- 239000000243 solution Substances 0.000 claims description 39
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- 238000000034 method Methods 0.000 claims description 31
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- 230000008569 process Effects 0.000 claims description 23
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
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- 238000010041 electrostatic spinning Methods 0.000 claims description 10
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 2
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Images
Classifications
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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
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
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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
- B01D2325/48—Antimicrobial properties
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a liquid-liquid membrane extraction efficient anti-pollution nanofiber composite membrane and a preparation method thereof. And preparing a PDMS selective layer on the PVDF/non-woven fabric nanofiber supporting layer by an electrostatic spraying technology so as to selectively extract organic matters. AgNPs materials or grafted Ag-MOFs materials grow in situ on the PDMS selection layer by a membrane modification method to prepare two different modification layers so as to achieve the aims of sterilization and stain resistance. The invention can effectively improve the long-term anti-pollution performance of the composite membrane, enables the membrane to keep excellent long-term organic matter mass transfer effect, and has excellent selectivity and long-term stability.
Description
Technical Field
The invention belongs to the field of high-salinity organic wastewater treatment, and particularly relates to a high-efficiency anti-pollution nanofiber composite membrane with biological pollution resistance, high mass transfer coefficient and high retention rate for liquid-liquid membrane extraction and a preparation method thereof.
Background
High-salt organic waste water is produced by various industrial processes, such as textile dyeing, pharmaceuticals, leather industry, petroleum refining, food processing, paper making, hydrometallurgy, animal husbandry, detergent manufacturing, etc., and is also present in road runoff water and landfill leachate. In industrial wastewater, main salt components are sulfate, sodium chloride, nitrate and phosphate, and in addition, the wastewater contains various organic compounds which are difficult to degrade, such as phenol, phenolic compounds, dyes, antibiotics, pesticides, artificial complexing agents, polycyclic aromatic hydrocarbons, medicines and the like, and the substances have strong acid-base property and high toxicity, and if the substances are not treated, the emission of the high-salt organic wastewater can cause serious environmental pollution. According to the latest environmental statistics annual report data of the department of ecological environmental protection, 25.6 million tons of sewage discharged by chemical raw materials and chemical product manufacturing industry in 2015 is the first discharge amount of industrial wastewater in China and is a main source of high-salinity organic wastewater. Because the industrial scale is rapidly enlarged in recent years, the high-salinity wastewater production in China accounts for 5% of the total wastewater amount, and the high-salinity wastewater production still increases at a rate of 2% every year, so the problems of treatment and discharge of the high-salinity organic wastewater are highly emphasized. Such waste water is difficult to treat in a conventional manner due to the presence of high concentrations of soluble salts and toxic organic contaminants, and organic components such as phenol are valuable reagents and should be recovered from the waste water. Therefore, the development of an efficient and environment-friendly method for treating and recovering high-salinity organic wastewater is an important subject.
The liquid-liquid membrane extraction process (aquous-aquous membrane extraction process) can be used for treating wastewater containing toxic components which are difficult to be treated by the conventional biological process. The liquid-liquid membrane extraction technology effectively combines a membrane separation technology and a biodegradation technology, and organic pollutants in the wastewater can enter a bioreactor through solution diffusion through a selective permeable membrane for subsequent biodegradation. Continuous biodegradation enables the concentration of organic matters on the microorganism side to be lower, and the organic matters are driven by concentration difference on two sides to permeate across membranes continuously. The liquid-liquid membrane extraction process achieves the simultaneous separation and biodegradation of organic and inorganic species, so the liquid-liquid membrane extraction process can remove or recover target compounds from wastewater streams, which is not possible with conventional biological processes.
However, the liquid-liquid membrane extraction process has some bottleneck problems, which limit its large-scale application, and membrane fouling, especially biological fouling of membranes, is a significant challenge for almost all membrane processes, and the liquid-liquid membrane extraction process is no exception. During long-term liquid-liquid membrane extraction operation, microorganisms will adhere and gather on the surface of the extraction membrane facing the bioreactor, increasing the mass transfer resistance of the membrane and significantly reducing the mass transfer rate of the process (30% of the initial mass transfer rate). Unlike the conventional membrane bioreactor process, in the liquid-liquid membrane extraction process, although no external pressure forces the surface of the membrane to accumulate a large amount of microorganisms, which causes membrane pollution, since the only source of organic matters required for the growth and metabolism of microorganisms in the reactor is the organic matters passing through the membrane, the microorganisms spontaneously accumulate on the surface of the membrane, inevitably adhere and accumulate a thick layer of biological membrane on the surface of the membrane, and finally cause the increase of membrane resistance and the reduction of organic mass transfer coefficient.
Disclosure of Invention
In order to solve the problems, the invention provides a high-efficiency anti-pollution nanofiber composite membrane with excellent anti-pollution performance, excellent long-term organic matter mass transfer efficiency and excellent selectivity and a preparation method thereof. Aiming at the liquid-liquid membrane extraction process, a PVDF nanofiber supporting layer with a double-layer structure is constructed on a non-woven fabric supporting layer through an electrostatic spinning method, and a PDMS (polydimethylsiloxane) selecting layer is constructed on the PVDF/non-woven fabric supporting layer through an electrostatic spraying technology. The PDMS selective layer is modified by a modification technology to prepare two different modification layers, so that the membrane has the capability of sterilization and stain resistance. The multilayer structure composite membrane prepared by the method aiming at the liquid-liquid membrane extraction process can effectively improve the biological pollution resistance of the composite membrane, so that the membrane has good long-term mass transfer effect, a reliable new method is provided for the preparation of the high-efficiency anti-pollution composite extraction membrane, and the application of the liquid-liquid membrane extraction technology in practice is promoted.
In order to achieve the purpose, the invention is obtained by the following technical scheme:
the efficient anti-pollution nanofiber composite membrane is a multilayer membrane structure formed by a PVDF/non-woven fabric nanofiber supporting layer, a PDMS (polydimethylsiloxane) selecting layer and an anti-pollution modification layer, wherein the nanofiber supporting layer is a high-porosity PVDF/non-woven fabric nanofiber supporting layer formed on a non-woven fabric through an electrostatic spinning technology. The compact and nonporous PDMS layer on the upper layer of the support layer is a selection layer of the composite membrane, and the upper layer of the PDMS selection layer is an anti-pollution modification layer. Through the hot pressing process, the tight combination between PVDF and non-woven fabrics can be effectively ensured. The PDMS selective layer can keep good adhesion with the PVDF/non-woven fabric supporting layer in a cross-linking film forming process by means of self viscosity. The modification process involves in-situ generation and covalent bonding, and the strong interaction makes the modified layer tightly combined on the PDMS selective layer. In subsequent long-term tests, the phenomena of loose adhesion or partial falling of all layers of the composite film do not occur.
A preparation method of a high-efficiency anti-pollution nanofiber composite membrane aiming at liquid-liquid membrane extraction adopts electrostatic spinning, electrostatic spraying and modification technologies to prepare the nanofiber composite membrane, and comprises the following steps:
step 1, preparing a PVDF/non-woven fabric nanofiber supporting layer:
preparing a lower layer of coarse nanofibers on the non-woven fabric by electrostatic spinning of 8 wt% of PVDF solution (the coarse nanofibers are coarse PVDF nanofibers with the average nanofiber diameter of 171 +/-16 nm), then obtaining upper layer of fine nanofibers on the lower layer of coarse nanofibers by electrostatic spinning of 3 wt% of PVDF solution (the fine nanofibers are ultrafine PVDF nanofibers with the average nanofiber diameter of 85 +/-24 nm), and preparing a PVDF/non-woven fabric nanofiber supporting layer with high porosity;
placing the PVDF/non-woven fabric nanofiber supporting layer obtained in the step 1 in a mixed solution of water and glycerol for more than 12 hours to ensure that gaps of the supporting layer are fully filled with the mixed solution;
forming a PDMS selection layer on the upper part of the PVDF/non-woven fabric nanofiber supporting layer pretreated in the step 2 by using a 30 wt% PDMS solution through an electrostatic spray printing technology, and crosslinking for 24 hours at 80 ℃ to obtain a PVDF/PMDS/non-woven fabric nanofiber composite membrane with a three-layer structure;
placing the PDMS/PVDF/non-woven fabric nanofiber composite membrane obtained in the step 3 in a mixed solution of water and absolute ethyl alcohol for five minutes to ensure that the membrane is wetted;
and 5, preparing the anti-pollution modified layer by selecting one of the following two modes:
mode 1: modifying the surface of the nanofiber composite membrane obtained in the step 4, putting the membrane into a mixed solution of dopamine hydrochloride, trihydroxymethyl aminomethane, copper sulfate pentahydrate and hydrogen peroxide, oscillating for one hour, washing off redundant or weakly anchored polydopamine on the surface of the membrane, and placing the polydopamine pre-modified membrane into a solution prepared from 0.5 wt% AgNO3Adding ammonia water dropwise into a silver-containing aqueous solution consisting of 0.02 wt% of ethanol until the solution becomes clear from turbidity and keeps unchanged, adding 1 wt% of glucose after 5min to accelerate silver mirror reaction, standing for 20min to enable AgNPs to be uniformly deposited on the surface of a polydopamine coating film, adhering the film to the bottom of a container in the process, sealing the film side by using an adhesive tape to ensure that modification reaction is only carried out on the film surface, and drying the modified film for one hour at the temperature of 100 ℃ to obtain the high-efficiency anti-pollution nanofiber composite film with a multilayer structure;
mode 2: modifying the surface of the nanofiber composite membrane obtained in the step 4, and putting the membrane into a mixed solution of dopamine hydrochloride, tris (hydroxymethyl) aminomethane, copper sulfate pentahydrate, hydrogen peroxide, mercapto-polyethylene glycol-carboxyl and Ag-MOFs materials for oscillation for one hour; the film is stuck to the bottom of the container in the process, and the film side is sealed by an adhesive tape so as to ensure that the modification reaction is only carried out on the surface of the film; and drying the modified membrane for one hour at the temperature of 100 ℃ to obtain the high-efficiency anti-pollution nanofiber composite membrane with a multilayer structure.
The 8 wt% PVDF solution in the step 1 is prepared by adding 8 wt% PVDF powder into a mixed solvent of N, N-Dimethylformamide (DMF) and acetone, wherein the mass ratio of the DMF to the acetone is 8: 2, adding 0.008 wt% of lithium chloride (LiCl) to enhance the conductivity of the solution, and stirring until the solution is dissolved; the 3 wt% PVDF solution is prepared by adding 3 wt% PVDF powder into a mixed solvent of N, N-Dimethylformamide (DMF) and acetone, wherein the mass ratio of DMF to acetone is 4: 6, adding 0.01 wt% of lithium chloride (LiCl) to enhance the conductivity of the solution, and stirring until the solution is dissolved; the nano-fiber supporting layer is thermally treated for 0.5 hour at the temperature of 150 ℃ and 170 ℃ under the condition of 1-2bar so as to ensure the bonding tightness of the PVDF nano-fiber and the non-woven fabric.
The mass ratio of water to glycerol in the step 2 is 1: 4, the step is to ensure that the upper layer of PDMS does not invade into the porous support layer, so the proportion of glycerol needs to ensure that the PDMS does not invade and the adhesion on the surface of the support layer is not affected by the adhesion of the PDMS selective layer and the support layer.
And 3, adding 30 wt% of PDMS monomer and crosslinking curing agent (the mass ratio of the monomer to the crosslinking curing agent is 10: 1) into n-hexane in the PDMS solution in the step 3, and uniformly stirring.
The mass ratio of water to absolute ethyl alcohol in the step 4 is 1: 1, ensuring complete wetting of the membrane.
The concentration of each component of the mixed solution in the mode 1 in the step 5 is as follows: 2g/L of dopamine hydrochloride, 1.2g/L of tris (hydroxymethyl) aminomethane, 0.8g/L of copper sulfate pentahydrate, 2.22g/L of hydrogen peroxide, 0.5 wt% of silver nitrate, 0.02 wt% of absolute ethyl alcohol and 1 wt% of glucose.
The concentration of each component of the mixed solution in the mode 2 in the step 5 is as follows: 2g/L of dopamine hydrochloride, 1.2g/L of tris (hydroxymethyl) aminomethane, 0.8g/L of copper sulfate pentahydrate, 2.22g/L of hydrogen peroxide, 1g/L of mercapto-polyethylene glycol-carboxyl and 0.05 wt% of Ag-MOFs material.
The invention also provides an application of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction, and the efficient anti-pollution nanofiber composite membrane is applied to treatment of high-salinity organic wastewater, such as wastewater generated in processes of textile dyeing, pharmacy, leather industry, petroleum refining, food processing, papermaking, hydrometallurgy, animal husbandry, detergent manufacturing industry, road runoff water, garbage leachate and the like.
The invention has the beneficial effects that:
the modified layer/PDMS/PVDF/non-woven fabric nano-fiber composite membrane with a multilayer structure, which is prepared in the invention and applied to the liquid-liquid membrane extraction process, can effectively improve the long-term anti-pollution performance of the composite membrane, so that the membrane can keep long-term excellent organic matter mass transfer effect, and has excellent selectivity and excellent long-term stability. Secondly, the invention provides a new scheme for the preparation of the liquid-liquid membrane extraction high-efficiency anti-pollution nanofiber composite membrane.
Drawings
In order to make the purpose, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1: the preparation process of the nanofiber composite membrane is schematically shown, wherein an unmodified membrane, an AgNPs modified membrane and an Ag-MOFs modified membrane are respectively named as # M0, # M1 and # M2;
FIG. 2: composite membrane planar Scanning Electron Microscope (SEM) images and energy dispersive X-ray spectroscopy (EDX) images, wherein A, B is a plan view of nanofiber composite membrane # M0 at different magnifications; c is the surface EDX image of nanofiber composite film # M0; D. e is a plan view of the nanofiber composite membrane # M1 at different magnifications; f is the surface EDX image of nanofiber composite membrane # M1; G. h is a plan view of the nanofiber composite membrane # M2 with different magnification; i is an EDX image of the surface of the nanofiber composite membrane # M2;
FIG. 3: the liquid-liquid membrane extraction testing device is used for testing the mass transfer effect of the organic matter of the composite membrane, wherein the left side feeding liquid is 1L of pure water (1g/L NaCl, 1g/L phenol), and the right side receiving liquid is 1L of deionized water or activated sludge solution;
FIG. 4: the mass transfer effect of the composite membrane for water-water membrane extraction of phenol;
FIG. 5: the mass transfer effect of the composite membrane for extracting phenol by a water-activated sludge membrane for a long time.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or under recommended conditions.
Example 1
PVDF/nonwoven support layers were prepared by electrospinning 8% and 3 wt% PVDF casting solutions onto nonwoven fabrics. 8 wt% PVDF solution is prepared by adding 8 wt% PVDF powder into a mixed solvent of N, N-Dimethylformamide (DMF) and acetone, wherein the mass ratio of DMF to acetone is 8: 2, adding 0.008 wt% of lithium chloride (LiCl) to enhance the conductivity of the solution, and stirring until the solution is dissolved; the 3 wt% PVDF solution is prepared by adding 3 wt% PVDF powder into a mixed solvent of N, N-Dimethylformamide (DMF) and acetone, wherein the mass ratio of DMF to acetone is 4: 6, adding 0.01 wt% of lithium chloride (LiCl) to enhance the conductivity of the solution, and stirring until dissolved. The PVDF/nonwoven support layer was hot pressed at a temperature of 155 ℃ for 30 minutes to ensure the integrity and mechanical strength of the base film. And then, the PVDF/non-woven fabric support layer is pre-wetted by a mixed solution of deionized water and glycerol (the weight ratio is 1: 4), so that the invasion of PDMS can be reduced during PDMS electric spraying. In the electrospray coating process, a prewetted PVDF base film is placed on a spinner drum, and a n-hexane solution containing 30 wt% PDMS (monomer and curing agent 10: 1(wt)) is electrosprayed on the surface of the PVDF base film. In the process of electrospraying solvent from needle to roller, n-hexane is completely evaporated, monomer and solidifying agent are deposited on the surface of PVDF base film in the form of film, and a thin and defect-free PDMS selective layer is deposited on the surface of PVDF base film. The composite film was cured for 24h at 80 ℃ after 40 minutes of electrostatic spraying to ensure complete PDMS crosslinking. To obtain the nanofiber composite membrane # M0.
Example 2
The nanofiber composite membrane # M0 obtained in example 1 was subjected to surface modification. The pre-wetted raw membrane # M0 with an aqueous ethanol solution was immersed in the prepared aqueous dopamine solution (2 g/L dopamine hydrochloride, 1.2g/L tris, 0.8g/L copper sulfate pentahydrate, 2.22g/L hydrogen peroxide) and shaken for 1h to obtain a polydopamine pre-activated membrane (# M0-D). After rinsing the polydopamine excess and weakly anchored to the membrane surface with deionized water, dopamine coated membrane # M0-D was placed in an aqueous silver-containing solution (0.5 wt% AgNO)3And 0.02 wt% ethanol), aqueous ammonia was added dropwise until the solution became clear from turbidity and remained unchanged. Adding glucose (1 wt%) after 5min, and accelerating silver mirror reactionAnd standing for 20min to enable AgNPs to be uniformly deposited on the surface of # M0-D. The film was glued to the bottom of the container and the film side was sealed with tape to ensure that the modification reaction only proceeded on the film surface. The modified film was dried at 100 ℃ for 1h to give an AgNPs modified film # M1. The electrospun original membrane # M0 prewetted with ethanol aqueous solution was immersed in the prepared Ag-MOFs dopamine mixed aqueous solution (dopamine hydrochloride 2g/L, tris 1.2g/L, copper sulfate pentahydrate 0.8g/L, hydrogen peroxide 2.22g/L, mercapto-polyethylene glycol-carboxyl 1g/L and Ag-MOFs material 0.05 wt%) and shaken for 1 h. The film was glued to the bottom of the container and the film side was sealed with tape to ensure that the modification reaction only proceeded on the film surface. The modified film was dried at 100 ℃ for 1h to obtain Ag-MO Fs modified film # M2.
Example 3
After the nanofiber composite membranes # M0, # M1 and # M2 obtained in examples 1 and 2 were subjected to a continuous phenol mass transfer test for 6 hours using a water-water membrane extraction apparatus as shown in FIG. 3, the results of the continuous phenol mass transfer test were shown in FIG. 4, in which the salt rejection rates of all three composite membranes were 99% or more, and higher phenol k was obtained0The value (# M0 is 38.7. + -. 0.9X 10)–7M/s, # M1 was 29.2. + -. 0.17X 10–7M/s, # M2 was 33.5. + -. 0.03X 10–7m/s). The embodiment shows that the composite membrane prepared by the invention has excellent organic matter mass transfer effect and selectivity.
Example 4
As a result of conducting a 12-day continuous phenol mass transfer test using the nanofiber composite membranes # M0, # M1 and # M2 obtained in examples 1 and 2 in a water-activated sludge membrane extraction apparatus as shown in FIG. 3, as shown in FIG. 5, the mass transfer coefficients of both modified membranes # M1 and # M2 after a 12-day long-term test were higher than that of # M0(# M0: 23.2. + -. 0.9X 10%–7M/s, # M1 was 27.2. + -. 0.17X 10–7M/s, # M2 was 33.1. + -. 0.03X 10–7m/s). The embodiment shows that the high-efficiency anti-pollution nanofiber composite membrane prepared by the method can effectively improve the long-term anti-pollution performance of the composite membrane, so that the membrane can keep long-term excellent organic matter mass transfer effect, and has excellent selectivity and excellent long-term stability.
In conclusion, the multilayer-structured modified layer/PDMS/PVDF/non-woven high-efficiency anti-pollution nanofiber composite membrane prepared by electrostatic spinning, electrostatic spraying and membrane modification methods in the invention has excellent anti-pollution performance, excellent organic matter mass transfer efficiency, excellent selectivity and excellent long-term stability, and provides a reliable way for preparing the high-efficiency anti-pollution composite extraction membrane.
Claims (9)
1. The efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction is characterized in that: the nanofiber composite membrane is of a multilayer membrane structure consisting of a PVDF/non-woven fabric nanofiber supporting layer, a PDMS selecting layer and an anti-pollution modification layer, wherein the PVDF/non-woven fabric nanofiber supporting layer is formed on a non-woven fabric through an electrostatic spinning method, and then the PVDF/non-woven fabric nanofiber supporting layer with high porosity is formed through hot pressing treatment, the PDMS selecting layer is prepared through an electrostatic spraying technology, and the anti-pollution modification layer is obtained through a surface modification process of the membrane.
2. A method for preparing the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction according to claim 1, wherein the method comprises the following steps: the preparation method of the nanofiber composite membrane by adopting the electrostatic spinning, electrostatic spraying and membrane modification technologies comprises the following steps:
step 1, preparing a PVDF/non-woven fabric nanofiber supporting layer:
preparing lower-layer coarse nanofibers on the non-woven fabric by electrostatic spinning of 8 wt% of PVDF solution, and then obtaining upper-layer fine nanofibers on the lower-layer coarse nanofibers by electrostatic spinning of 3 wt% of PVDF solution, so as to prepare a PVDF/non-woven fabric nanofiber supporting layer with high porosity;
step 2, pretreatment of the PVDF/non-woven fabric nanofiber supporting layer:
placing the PVDF/non-woven fabric nanofiber supporting layer obtained in the step 1 in a mixed solution of water and glycerol for more than 12 hours to ensure that gaps of the supporting layer are fully filled with the mixed solution;
step 3, preparing a PDMS selection layer:
forming a PDMS selection layer on the upper part of the PVDF/non-woven fabric nanofiber supporting layer pretreated in the step 2 by using a 30 wt% PDMS solution through an electrostatic spray printing technology, and crosslinking for 24 hours at 80 ℃ to obtain a PDMS/PVDF/non-woven fabric nanofiber composite membrane with a three-layer structure;
step 4, pretreating the PDMS/PVDF/non-woven fabric nanofiber composite membrane:
placing the PDMS/PVDF/non-woven fabric nanofiber composite membrane obtained in the step 3 in a mixed solution of water and absolute ethyl alcohol for five minutes to ensure that the membrane is wetted;
and 5: the preparation of the anti-pollution modified layer is carried out by selecting one of the following two modes:
mode 1: modifying the surface of the nanofiber composite membrane obtained in the step 4, putting the membrane into a mixed solution of dopamine hydrochloride, trihydroxymethyl aminomethane, copper sulfate pentahydrate and hydrogen peroxide, oscillating for one hour, washing off redundant or weakly anchored polydopamine on the surface of the membrane, and placing the polydopamine pre-modified membrane into a solution prepared from 0.5 wt% AgNO3And 0.02 wt% ethanol, and ammonia water is added dropwise until the solution becomes clear from turbidity and remains unchanged; adding 1 wt% of glucose after 5min, accelerating silver mirror reaction, standing for 20min to enable AgNPs to be uniformly deposited on the surface of the polydopamine pre-modified membrane; the film is stuck to the bottom of the container in the process, and the film side is sealed by an adhesive tape so as to ensure that the modification reaction is only carried out on the surface of the film; drying the modified membrane for one hour at the temperature of 100 ℃ to obtain the high-efficiency anti-pollution nanofiber composite membrane with a multilayer structure;
mode 2: modifying the surface of the nanofiber composite membrane obtained in the step 4, and putting the membrane into a mixed solution of dopamine hydrochloride, tris (hydroxymethyl) aminomethane, copper sulfate pentahydrate, hydrogen peroxide, mercapto-polyethylene glycol-carboxyl and Ag-MOFs materials for oscillation for one hour; the film is stuck to the bottom of the container in the process, and the film side is sealed by an adhesive tape so as to ensure that the modification reaction is only carried out on the surface of the film; and drying the modified membrane for one hour at the temperature of 100 ℃ to obtain the high-efficiency anti-pollution nanofiber composite membrane with a multilayer structure.
3. The preparation method of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction as claimed in claim 2, wherein: in the step 1, 8 wt% of PVDF solution is prepared by adding 8 wt% of PVDF powder into a mixed solvent of N, N-dimethylformamide and acetone, wherein the mass ratio of DMF to acetone is 8: 2, adding 0.008 wt% of lithium chloride to enhance the conductivity of the solution, and stirring until the solution is dissolved; the 3 wt% PVDF solution is prepared by adding 3 wt% PVDF powder into a mixed solvent of N, N-dimethylformamide and acetone, wherein the mass ratio of DMF to acetone is 4: 6, adding 0.01 wt% of lithium chloride to enhance the conductivity of the solution, and stirring until the solution is dissolved; the nano-fiber supporting layer is thermally treated for 0.5 hour at the temperature of 150 ℃ and 170 ℃ under the condition of 1-2bar so as to ensure the bonding tightness of the PVDF nano-fiber and the non-woven fabric.
4. The preparation method of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction as claimed in claim 2, wherein: the mass ratio of water to glycerol in the step 2 is 1: 4.
5. the preparation method of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction as claimed in claim 2, wherein: the PDMS solution in the step 3 is prepared by mixing 30 wt% of PDMS monomer and a crosslinking curing agent according to a mass ratio of 10: 1, adding the mixture into n-hexane, and uniformly stirring.
6. The preparation method of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction as claimed in claim 2, wherein: the mass ratio of water to absolute ethyl alcohol in the step 4 is 1: 1.
7. the preparation method of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction as claimed in claim 2, wherein: the concentration of each component of the mixed solution in the mode 1 in the step 5 is as follows: 2g/L of dopamine hydrochloride, 1.2g/L of tris (hydroxymethyl) aminomethane, 0.8g/L of copper sulfate pentahydrate, 2.22g/L of hydrogen peroxide, 0.5 wt% of silver nitrate, 0.02 wt% of absolute ethyl alcohol and 1 wt% of glucose.
8. The preparation method of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction as claimed in claim 4, wherein: the concentration of each component of the mixed solution in the mode 2 in the step 5 is as follows: 2g/L of dopamine hydrochloride, 1.2g/L of tris (hydroxymethyl) aminomethane, 0.8g/L of copper sulfate pentahydrate, 2.22g/L of hydrogen peroxide, 1g/L of mercapto-polyethylene glycol-carboxyl and 0.05 wt% of Ag-MOFs material.
9. The application of the efficient anti-pollution nanofiber composite membrane for liquid-liquid membrane extraction as claimed in claim 1, wherein: the efficient anti-pollution nanofiber composite membrane is applied to treatment of high-salinity organic wastewater.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119836A (en) * | 2022-12-26 | 2023-05-16 | 南开大学 | Bioreactor for treating organic pollutants in toxic sewage and application method thereof |
| CN116747715A (en) * | 2023-04-14 | 2023-09-15 | 浙江大学 | High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110311822A1 (en) * | 2010-06-16 | 2011-12-22 | Board Of Regents, The University Of Texas System | Hollow nanoparticles and nanocomposites and methods of making hollow nanoparticles and nanocomposites |
| CN108938596A (en) * | 2018-08-03 | 2018-12-07 | 宁夏医科大学 | A kind of CPPs/NGR modification medicament-carried nano gold stick and the preparation method and application thereof |
| CN109796616A (en) * | 2019-01-11 | 2019-05-24 | 西北大学 | The method and application of a kind of Biomimetic Polymers and the double Biomimetic Polymers coatings of production durability |
| CN111871226A (en) * | 2020-01-22 | 2020-11-03 | 南开大学 | Nanofiber composite membrane for liquid-liquid membrane extraction process and preparation method thereof |
| CN112717207A (en) * | 2020-12-15 | 2021-04-30 | 山东大学 | Long-acting antibacterial multifunctional coating based on bionic dopamine and preparation method and application thereof |
-
2021
- 2021-11-09 CN CN202111319849.1A patent/CN114210210B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110311822A1 (en) * | 2010-06-16 | 2011-12-22 | Board Of Regents, The University Of Texas System | Hollow nanoparticles and nanocomposites and methods of making hollow nanoparticles and nanocomposites |
| CN108938596A (en) * | 2018-08-03 | 2018-12-07 | 宁夏医科大学 | A kind of CPPs/NGR modification medicament-carried nano gold stick and the preparation method and application thereof |
| CN109796616A (en) * | 2019-01-11 | 2019-05-24 | 西北大学 | The method and application of a kind of Biomimetic Polymers and the double Biomimetic Polymers coatings of production durability |
| CN111871226A (en) * | 2020-01-22 | 2020-11-03 | 南开大学 | Nanofiber composite membrane for liquid-liquid membrane extraction process and preparation method thereof |
| CN112717207A (en) * | 2020-12-15 | 2021-04-30 | 山东大学 | Long-acting antibacterial multifunctional coating based on bionic dopamine and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119836A (en) * | 2022-12-26 | 2023-05-16 | 南开大学 | Bioreactor for treating organic pollutants in toxic sewage and application method thereof |
| CN116119836B (en) * | 2022-12-26 | 2024-03-08 | 南开大学 | Bioreactor for treating organic pollutants in toxic sewage and application method thereof |
| CN116747715A (en) * | 2023-04-14 | 2023-09-15 | 浙江大学 | High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof |
| CN116747715B (en) * | 2023-04-14 | 2024-01-23 | 浙江大学 | High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof |
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