CN112744899B - MXene membrane for treating antibiotic wastewater and preparation method and application thereof - Google Patents
MXene membrane for treating antibiotic wastewater and preparation method and application thereof Download PDFInfo
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- CN112744899B CN112744899B CN202011522747.5A CN202011522747A CN112744899B CN 112744899 B CN112744899 B CN 112744899B CN 202011522747 A CN202011522747 A CN 202011522747A CN 112744899 B CN112744899 B CN 112744899B
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
Abstract
The invention discloses an MXene membrane for treating antibiotic wastewater and a preparation method and application thereof. Belongs to the field of two-dimensional nano-film preparation technology and antibiotic wastewater treatment. The application comprises the following steps: (1) Putting the two-dimensional MXene membrane into an electrocatalytic membrane reaction device, and then introducing the antibiotic wastewater to be treated into the water inlet side; (2) And (2) detecting the effluent of the step (1) by using high performance liquid chromatography. The MXene electrochemical reduction membrane has high removal rate on Florfenicol (FLO), chloramphenicol (CAP), thiamphenicol (TMP), nitrofurazone (NFZ) and Ofloxacin (OFX), and effectively disinfects the antibacterial activity of antibiotic wastewater. Compared with an MXene membrane separation system without potential, the MXene electrochemical reduction membrane system is more stable, and the service life of MXene is longer.
Description
Technical Field
The invention belongs to the field of nano-film and antibiotic wastewater treatment, and particularly relates to an MXene film catalysis technology for treating antibiotic wastewater.
Background
Most antibiotics are slightly soluble in water, have poor biodegradability, and are difficult to degrade by traditional wastewater treatment techniques. In order to effectively eliminate antibiotic antibacterial activity and prevent the spread of resistance genes, the development of new technologies and new materials for efficiently processing antibiotics is urgently needed, and the economy, controllability and stability of the antibiotics are realized.
The electrochemical reduction method is to directly or indirectly remove pollutants or reduce the toxicity of the pollutants at a cathode under the action of an external electric field, and control a reduction path and a reduction product through voltage. Other reagents are not needed to be added in the using process, and secondary pollution is avoided. The characteristics of high efficiency, controllability and environmental friendliness of the electrochemical reduction technology enable the electrochemical reduction technology to have great potential utilization value in the wastewater treatment process. However, the efficiency of treating low-concentration wastewater in the electrochemical reduction process is often low. While antibiotics are often present in the environment on the ng-mug scale. The membrane filtration technology has the advantages of rapid separation and concentration of pollutants, small influence on the environment and the like, and has received wide attention. However, the membrane pollution problem during the separation process can greatly reduce the membrane separation performance and increase the energy consumption. In addition, the treatment of concentrate produced during membrane separation is also particularly difficult. Therefore, the combination of electrochemical reduction and membrane separation technology is an optimal mode for solving the problems of low efficiency of electrochemical low-concentration wastewater treatment and difficult concentrated water treatment in the membrane separation process.
In recent years, two-dimensional MXene membranes are widely concerned due to the advantages of simple preparation method, good hydrophilicity, strong conductivity and the like, and show great application potential in the separation field.
Disclosure of Invention
In order to improve the defect that MXene is easy to oxidize in water and realize the breakthrough of an MXene membrane in the field of water treatment, the invention aims to provide an MXene membrane catalysis technology for treating antibiotic wastewater, wherein the MXene membrane is used as a cathode to reduce antibiotics on the surface of the MXene membrane in situ while separating and concentrating the antibiotics, so that the antibacterial activity of concentrated antibiotic water is eliminated.
The purpose of the invention is realized by the following technical scheme.
Firstly, the invention provides an MXene membrane catalysis method for treating antibiotic wastewater, which comprises the following steps:
(1) Putting the two-dimensional MXene membrane into an electrocatalytic membrane reaction device, and then introducing the antibiotic wastewater to be treated into the water inlet side;
(2) And (2) detecting the effluent of the step (1) by using high performance liquid chromatography.
The preferred method comprises the steps of:
(1) Putting the two-dimensional MXene membrane into an electrocatalytic membrane reaction device, and adding antibiotics and a background electrolyte solution into the water inlet side;
(2) Pushing an antibiotic solution to be degraded into the reaction system through a peristaltic pump;
(3) Applying a voltage to the reaction system using the electrochemical workstation;
(4) Collecting the penetrating fluid on the water outlet side, and detecting the concentration of the antibiotics by using high performance liquid chromatography.
Preferably, the MXene membrane in the step (1) is a flat membrane and comprises a support layer and a functional layer; the functional layer is an ultrathin compact film formed by MXene, and the thickness of the ultrathin compact film is about 50-800 nm;
the supporting layer can be made of any one of PTFE, PA and PVDF, the PVDF material is preferably used as the supporting layer, and the pore diameter of the supporting layer is preferably mum.
Preferably, the preparation method of the two-dimensional MXene film in the step (1) comprises the following steps:
(a) Adding MAX powder into a plastic beaker, slowly dripping HF into the plastic beaker while stirring, stirring and etching, centrifugally cleaning, and drying to obtain MXene powder;
(b) Dispersing the etched MXene powder in a solvent, stirring for intercalation, centrifuging, washing, centrifuging after ultrasonic treatment, and taking supernatant to obtain single-layer or few-layer MXene nanosheet colloid dispersion liquid;
(c) Diluting the colloidal dispersion liquid obtained in the step (b), filtering the diluted colloidal dispersion liquid on a PVDF basement membrane by adopting an ultrafiltration cup, and drying the PVDF basement membrane in vacuum to obtain the MXene membrane.
Preferably, the MAX powder in preparation step (a) is Ti3AlC2。
Preferably, the PVDF membrane prepared in the step (c) has a pore size of 0.05-3 μm.
The two-dimensional MXene film prepared by the method is firmly combined with the base film, has no crack on the surface, and has good flexibility and mechanical property.
Preferably, the electrocatalytic membrane reaction device in the step (1) is characterized in that: a working electrode, a counter electrode and a reference electrode are adopted.
Preferably, polytetrafluoroethylene materials are adopted as a reactor in the step (1), and the reactor consists of a water inlet side, a membrane and a water outlet side; the water inlet side is a base, the reference electrode and the counter electrode are uniformly distributed on the base, and the MXene membrane surface faces downwards, so that the influence of bubbles generated in the electrochemical reaction process on mass transfer can be prevented.
Preferably, the working electrode is an MXene film, and a certain potential is applied to the MXene film by a potentiostatic method.
Preferably, the counter electrode is any one of a titanium mesh, a copper mesh, a stainless steel mesh and a platinum mesh, and the platinum mesh is preferred.
Preferably, the concentration of the antibiotic in the step (2) is 1-50 ppm.
Preferably, the applied potential in step (3) may be-1.0V to-2.0V, and preferably the applied potential is-1.5V.
The beneficial effects of the invention compared with the prior art comprise:
according to the MXene membrane catalysis technology for treating the antibiotic wastewater, disclosed by the invention, the two-dimensional MXene membrane is used for separating the antibiotics, and the antibiotics are reduced and degraded on the surface of the MXene membrane in situ, so that the antibacterial activity of the antibiotic wastewater is effectively reduced, and meanwhile, the stability of the MXene membrane in an aqueous solution is greatly improved. The MXene electrochemical reduction membrane system has great application value in the practical antibiotic wastewater treatment process.
The MXene electrochemical reduction membrane has high removal rate on Florfenicol (FLO), chloramphenicol (CAP), thiamphenicol (TMP), nitrofurazone (NFZ) and Ofloxacin (OFX), and effectively disinfects the antibacterial activity of antibiotic wastewater. Compared with the MXene membrane separation system without applied potential, the MXene electrochemical reduction membrane system is more stable, and the service life of the MXene is longer.
Drawings
FIG. 1 is a schematic view of the structure of an electrocatalytic membrane reactor of the present invention, wherein (1) -water outlet; (2) -an MXene film; (3) -a PVDF base film; (4) -a counter electrode; (5) -a reference electrode; (6) -a water inlet.
FIG. 2 is a bar graph of the removal of five different antibiotics.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a two-dimensional MXene film comprises the following steps:
(a) 1-10 g of Ti3AlC2Adding the powder into a plastic beaker, then slowly dripping 20-200mL of 50% HF into the beaker, stirring and reacting for 12-48 h, centrifugally washing under the condition of 2000-10000 rpm until the pH value of the upper layer is stable, and then freezingDrying for 12-48 h to obtain Ti3C2TxPowder;
(b) Adding 10-200 mLDMSO into 1-10 gTi3C2TxStirring the powder for 12-48 h, centrifuging and washing for four times, adding 20-1000 mL of water, performing ultrasonic treatment for 1-5 h, centrifuging for 1-5 h at 2000-10000 rpm, and taking supernatant to obtain MXene nanosheet colloid dispersion liquid;
(c) And (b) taking 20-60 mL of MXene colloidal dispersion liquid obtained in the step (b), using an ultrafiltration cup, applying Ar to the pressure of 0.1-0.3 MPa, stacking MXene nanosheets on a PVDF basement membrane with the aperture of 0.05-3 mu m and the diameter of 5-10 mm, and drying in a vacuum drying oven at 30-100 ℃ for 12-48 h to obtain the MXene membrane with the thickness of 50-800 nm.
Example 2
As shown in fig. 1, polytetrafluoroethylene is adopted as a reactor, (1) -a water outlet; (2) -an MXene film; (3) -a PVDF base film; (4) -a counter electrode; (5) -a reference electrode; (6) a water inlet for degrading different antibiotics, the reactor consisting of a water inlet side, a membrane and a water outlet side. The water inlet side is a base, the reference electrode and the counter electrode are uniformly distributed on the base, and the MXene membrane surface faces downwards, so that the influence of bubbles generated in the electrochemical reaction process on mass transfer can be prevented.
Working electrode MXene film, prepared by the method of example 1.
The counter electrode is a platinum mesh.
Example 3
The application of the two-dimensional MXene membrane in antibiotic wastewater treatment comprises the following steps:
the two-dimensional MXene membrane with the thickness of 50-800 nm is placed in the electro-catalytic membrane reaction device in the embodiment 2, an antibiotic solution is pushed into the water inlet side through a peristaltic pump, meanwhile, an electrochemical workstation is adopted to apply a potential of-1.5V by a constant potential method, a sample at the water outlet is collected, and the antibiotic concentration is detected by using high performance liquid chromatography.
As a result: the removal rate of the antibiotic ofloxacin in the effluent water is about 83 percent, and the removal rates of the other four antibiotics are as high as 95 percent to 100 percent, which is shown in a specific reference figure 2.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. An MXene membrane catalysis method for treating antibiotic wastewater is characterized by comprising the following steps:
(1) Putting the two-dimensional MXene membrane into an electrocatalytic membrane reaction device, and then introducing the antibiotic wastewater to be treated into the water inlet side;
(2) Detecting the effluent obtained in the step (1) by using a high performance liquid chromatography, wherein the antibiotics are reduced and degraded on the surface of the MXene membrane in situ while the two-dimensional MXene membrane is used for separating the antibiotics;
the preparation method of the two-dimensional MXene film comprises the following steps:
(a) 1-10 g of Ti3AlC2Adding the powder into a plastic beaker, then slowly dripping 20-200mL of 50% HF into the beaker, stirring and reacting for 12-48 h, centrifugally washing under the condition of 2000-10000 rpm until the pH value of the upper layer is stable, and then freeze-drying for 12-48 h to obtain Ti3C2TxPowder;
(b) Adding 10-200 ml of LDMSO into 1-10 g of Ti3C2TxStirring the powder for 12-48 h, centrifuging and washing for four times, adding 20-1000 mL of water, performing ultrasonic treatment for 1-5 h, centrifuging for 1-5 h at 2000-10000 rpm, and taking supernatant to obtain MXene nanosheet colloid dispersion liquid;
(c) And (c) taking 20-60 mL of MXene nanosheet colloidal dispersion liquid obtained in the step (b), applying 0.1-0.3 MPa pressure to the MXene nanosheet by using an ultrafiltration cup and Ar, stacking the MXene nanosheet on a PVDF basement membrane with the aperture of 0.05-3 mu m and the diameter of 5-10 mm, and drying the membrane in a vacuum drying oven at 30-100 ℃ for 12-48 h to obtain the MXene membrane with the thickness of 50-800 nm.
2. The method according to claim 1, wherein the antibiotic concentration in the antibiotic wastewater of step (1) is 1 to 50ppm.
3. The method of claim 1, wherein the electrocatalytic membrane reaction device in step (1) comprises: working electrode, counter electrode and reference electrode three-electrode system.
4. The method according to claim 1, wherein the polytetrafluoroethylene material is adopted as a reactor in the step (1), and the reactor consists of a water inlet side, a membrane and a water outlet side; the water inlet side is a base, the reference electrode and the counter electrode are uniformly distributed on the base, and the MXene membrane surface faces downwards, so that the influence of bubbles generated in the electrochemical reaction process on mass transfer is prevented.
5. The method of claim 3, wherein the potential of the MXene film is applied by potentiostatic method.
6. The method of claim 3, wherein the counter electrode is any one of a titanium mesh, a copper mesh, a stainless steel mesh, and a platinum mesh.
7. The method of claim 5, wherein the applied potential is between-1.0V and-2.0V.
8. The method of claim 7, wherein the applied potential is-1.5V.
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