CN115818769A - A continuous flow reaction device for photocatalytic treatment of antibiotic wastewater - Google Patents

Abstract

The invention relates to the field of photocatalytic treatment of water polluted environment, and relates to a continuous flow reaction device for photocatalytic treatment of antibiotic wastewater. The using method comprises the following steps: 1. weighing a certain amount of catalyst and dispersing the catalyst in the antibiotic wastewater. 2. And opening the magnetic stirrer to stir the solution to achieve adsorption-desorption balance. 3. And opening a peristaltic pump to lead the solution to flow into the continuous flow reactor, and carrying out catalytic reaction under light. 4. And collecting the solution after reaction, and introducing the solution into the continuous flow reactor again for a circulation experiment. 5. And detecting the solution after reaction, and calculating the removal rate of the antibiotics in the wastewater. The result shows that the continuous flow reactor has small size, high light transmittance and high reaction rate, the continuous flow can make the solution circularly react, and the research result has reference significance for using a continuous flow device for photocatalysis.

Description

A continuous flow reaction device for photocatalytic treatment of antibiotic wastewater

technical field

The invention belongs to the field of photocatalysis, in particular to a device for photocatalytic treatment of antibiotic wastewater, which uses continuous flow to carry out circular treatment of antibiotic wastewater.

Background technique

The information disclosed in this background section is only intended to increase the understanding of the general background of the present invention, and is not necessarily taken as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

The global survey report shows that from 2000 to 2015, the global antibiotic usage increased by 39%. If there is no effective policy control, it is estimated that the global antibiotic usage in 2030 will be 200% higher than that in 2015. Due to long-term use and accumulation, it has been considered as a chronic environmental pollutant. It interferes with the normal metabolism of the human body, changes the microbial community in the human body, and directly threatens human safety. In addition, antibiotic resistance genes can lead to drug-resistant bacteria, causing long-term harm to ecological health.

The widespread use of antibiotics has brought potential dangers to human health and the ecological environment. They mainly enter the environment through wastewater treatment plants, agricultural runoff, hospital sewage, and landfill leachate. Antibiotic residues have been detected in various water bodies. Therefore, , it is urgent to find a green, environmentally friendly, safe and effective method for the terminal treatment of antibiotic pollutants. As an advanced oxidation process, photocatalytic treatment technology has been widely used due to its advantages of low pollution, low cost, and complete degradation. The reaction produces active groups to accelerate the degradation process of organic matter, and degrades pollutants into non-toxic and harmless small molecules. The current research uses batch reactors, and the volume of the reactor is large, which leads to problems such as limited light transmission of the mixed solution and poor mass transfer effect.

Chinese patent document CN 113929175 A (application number 202111423360.9) discloses a tubular reaction device including an outer tube, an inner tube, a light source and a disturbance unit, the inner tube is made of transparent material, and the light source is arranged inside the inner tube , the outer layer tube is sheathed outside the inner layer tube, and the inner wall of the outer layer tube is coated with photocatalytic material; the turbulence unit is arranged between the outer layer tube and the inner layer tube. This type of device fixes the catalyst inside the device, and the photocatalyst material needs to be recoated periodically, which is time-consuming and labor-intensive.

Chinese patent document CN 216039085 U (application number 202122531566.5) discloses a continuous photocatalytic device for sewage treatment, including a box body, a catalyst adding device, a glass tube, a degradation tank, a xenon lamp light source and a centrifugal device, and the catalyst adding device is arranged in the box body and connected to the sewage inlet pipe; one end of the glass tube is connected to the catalyst adding device; the degradation tank is connected to the other end of the glass tube, and is provided with a sewage outlet pipe; the xenon light source is set in the box, and is located between the glass tube and Above the degradation tank; the centrifugal device is set on the sewage outlet pipe. The reaction of this type of device is carried out in the degradation pool. The volume of the degradation pool is large. When the solution is too much, the light transmittance of the mixed solution is low, which will affect the degradation effect of the reaction.

Chinese patent document CN114588855A (Application No. 202210085323.X) discloses a method and application of a continuous flow photocatalytic reaction device to regulate the catalyst activity. The method is to place the dilution of the target pollutant in the liquid storage tank, and connect the liquid storage tank and the photocatalytic reactor tightly through a silicone tube; through a single-channel peristaltic pump, the water inlet flow rate is controlled to be 5-30mL/min and the water outlet flow rate is 5-30mL/min. The flow rate is 1-15mL/min, and the average water flow rate is guaranteed to be 3-20mL/min. The device operates in a continuous flow state (serpentine pipeline), and the catalyst is continuously excited by ultraviolet light until the target pollutant is completely oxidized. However, the structure of the device is complex, and the catalyst needs to be coated, dried and fixed. The device needs to use multiple peristaltic pumps. The internal structure includes multiple photocatalytic nets, ultraviolet lamp groups, etc.

Chinese patent document CN114516673A (application number 202210031480.2) discloses a flat tube type continuous flow-photocatalytic oxidative degradation water treatment device, system and use method, including a flat tube reactor, the flat tube reactor has a multi-bend The multi-bend channel part is on the same plane, the multi-bend channel part has a medium inlet and a medium outlet, and the medium flows in from the inlet and out from the outlet, showing continuous flow state; the medium contains photocatalyst and oxidant; the upper part of the flat tubular reactor is provided with a light source, and the light source is vertically irradiated on the flat tubular reactor, and the irradiation range of the light source is not smaller than the area of the planar tubular reactor. However, the device uses a flat tube continuous flow structure, and it performs a photocatalytic oxidation reaction, which requires the introduction of photocatalysts and oxidants.

Contents of the invention

In order to solve the problems of poor light transmittance and low mass transfer due to the large volume of traditional reaction devices, the present invention proposes a continuous flow reaction device for rapid, safe and green treatment of antibiotic wastewater. The solution is mixed evenly with the catalyst in the stirring device, and enters the continuous reactor through the peristaltic pump for photocatalytic reaction. The continuous flow channel adopts millimeter or centimeter size, which improves the light transmittance of the mixed solution. The consumption of catalyst in the reaction process is guaranteed. The continuous flow reactor is suitable for a variety of catalysts to degrade a variety of antibiotics under different light sources. The selected catalysts can be bismuth tungstate, titanium dioxide, titanium silicon molecular sieve and other materials; the light source can be xenon lamp, mercury lamp, LED lamp, etc.; What can be treated can be various types of antibiotic wastewater such as quinolones, sulfonamides, tetracyclines, and β-lactams.

In order to achieve the above object, the present invention adopts the following technical solutions:

The first aspect of the present invention provides a continuous flow reaction device for photocatalytic treatment of antibiotic wastewater, comprising:

Magnetic stirring device, peristaltic pump, light source, continuous flow reactor, collection device;

The magnetic stirring device is sequentially connected with a peristaltic pump, a continuous flow reactor, and a collection device, and a light source is arranged above the continuous flow reactor;

The antibiotic wastewater containing the catalyst reaches the adsorption-desorption equilibrium in the magnetic stirring device;

The single residence time of the antibiotic wastewater containing the catalyst in the continuous flow reactor is 5-300s.

In order to adapt to the concept of photocatalytic treatment of antibiotic wastewater, which is economical, environmentally friendly and safe, the present invention designs a continuous flow reaction device in combination with research hotspots and the research basis of the research group, and provides a new idea for photocatalytic degradation of antibiotic wastewater.

A second aspect of the present invention provides a method for continuous flow reaction device treatment of antibiotic wastewater, comprising:

Disperse the catalyst in the antibiotic wastewater, and then stir it to make it reach the adsorption-desorption equilibrium;

Pumping the wastewater that has reached the adsorption-desorption balance into a continuous flow reaction device, and performing a photocatalytic reaction under light;

The solution after the reaction is collected, and re-introduced into the device for cyclic reaction to obtain the obtained product.

The third aspect of the present invention provides the application of the above device in the field of water treatment.

Beneficial effects of the present invention

(1) The continuous flow reaction device of the present invention can be used for fast, safe and green treatment of antibiotic wastewater. The solution is mixed evenly with the catalyst in the stirring device, and enters the continuous reactor through the peristaltic pump for photocatalytic reaction. The continuous flow channel adopts millimeter or centimeter size, which improves the light transmittance of the mixed solution. The consumption of catalyst in the reaction process is guaranteed.

(2) The device of this application is used for photocatalytic treatment of antibiotic wastewater, and the catalyst and antibiotic wastewater are directly mixed into the reactor, which is suitable for a variety of catalysts to treat a variety of antibiotic wastewater. Currently, the continuous flow reaction device is used for photocatalytic degradation of antibiotics. less research.

(3) The device of this application includes and is not limited to this type of planar structure, which can be designed according to the position and shape of the irradiation light source. The reactor used in the experiment is a whole piece of quartz glass, and the glass chip is numerically processed and sealed. The chip is 98mm long, 98mm wide, and 6mm high. It is easy to take, has a protective structure, and is made of solid material and is not easy to damage. It is designed as a serpentine channel to increase the light-receiving area and residence time of the solution. The interior is a square channel with a total length of 1.1m. Direct photocatalytic treatment of antibiotic wastewater, the microchannel structure improves the light transmittance, increases the mass transfer effect, and improves the degradation efficiency of antibiotic wastewater.

(4) Compared with the continuous flow reaction device of the existing serpentine pipeline, the continuous flow reaction device of the present application is made of glass microfluidic chip, which is more durable, and the continuous flow reaction channel adopts a smaller size, and the light is transparent. The conversion rate is high and the degradation effect is good. This device is used for photocatalytic treatment of antibiotic wastewater.

(5) The treatment method of the present invention is simple, practical and easy to popularize.

Description of drawings

The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention, and the exemplary embodiments and descriptions of the present invention are used to explain the present invention, and do not constitute improper limitations to the present invention.

Fig. 1 is a blank experiment;

The removal rate under the different flow rates of Fig. 2;

The removal rate under different catalyst concentrations of Fig. 3;

The removal rate under the different antibiotic concentrations of Fig. 4;

Fig. 5 is a schematic structural diagram of the device of the present invention.

Detailed ways

It should be noted that the following detailed description is exemplary and intended to provide further explanation of the present invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

A continuous flow device for photocatalytic treatment of antibiotic waste water, comprising a magnetic stirring device, a peristaltic pump, a light source, a continuous flow reactor, and a collection device.

Referring to the device connection schematic diagram of the present invention, the stirring device is composed of a magnetic stirrer, a beaker, and a magnet. The solution is stirred in the beaker, and the photocatalytic reaction is carried out after reaching the adsorption and desorption equilibrium; the peristaltic pump controls the fluid flow rate and regulates the solution flow rate; The continuous flow reactor can be processed and designed in a variety of shapes. The S-shaped channel used in the experiment has a long flow length. The channel adopts a millimeter size, which is conducive to the permeability of light. The solution channels are all laid under the light. ;The light source can be irradiated by various types of lights. The experiment uses a xenon lamp to degrade the antibiotic ofloxacin; the collection device uses a beaker, which can be re-introduced into the device for reaction; all parts are connected by silicone tubes , transparent and visible to observe the flow state.

The application of a method for photocatalytic treatment of antibiotic wastewater includes the use of multiple catalysts and the treatment of multiple antibiotics under multiple light sources.

A continuous flow device including research for photocatalytic treatment of antibiotic wastewater.

A continuous flow reactor design for performing reactions under a light source.

In some embodiments, the continuous flow reactor is suitable for a variety of catalysts to degrade a variety of antibiotics under different light sources. The catalyst selected can be bismuth tungstate, titanium dioxide, titanium silicon molecular sieve, carbon nitride, zinc oxide, bismuth oxide, One or more of tin oxide, cadmium sulfide, and metal doping, material loading, and reduction modification materials; the light source can be xenon lamp, mercury lamp, LED lamp, etc.; the treated can be quinolones, sulfonamides , Tetracyclines, β-lactams, macrolides, cephalosporins, aminoglycosides, lincosamides and various types of antibiotic wastewater.

In some embodiments, the stirring device, the reaction device and the collecting device are designed separately and connected by silicone tubes.

In some embodiments, a silicone tube connection device is used, and the size of the silicone tube is 3*4mm.

In some embodiments, it is suitable for the reaction of multiple catalysts corresponding to multiple antibiotics.

In some embodiments, the continuous flow reactor is made of quartz glass, which is transparent to light.

In some embodiments, the channels of the continuous flow reactor are millimeter-sized, 1.1 m long, 2 mm wide, and 2 mm high.

In some embodiments, the continuous flow reactor is an S-shaped channel.

In some embodiments, the solution flow rate is 0.1-50 mL/min.

In some embodiments, the single residence time of the solution in the reactor is 5-300s.

In some embodiments, the reaction is performed in a continuous channel, enabling a cyclic reaction.

The present invention will be described in further detail below in conjunction with specific examples. It should be pointed out that the specific examples are to explain rather than limit the present invention.

Embodiment 1: photocatalytic treatment antibiotic ofloxacin (OFX)

Use a peristaltic pump to pass the solution of ofloxacin (6mg/L) into the continuous flow reactor, carry out the photocatalytic reaction under the xenon lamp, and pass the solution after the reaction into the beaker. Pass into the continuous flow reactor for the next light reaction, and the sampled solution uses a UV-Vis spectrophotometer to measure the absorbance of OFX (290nm). When the peristaltic pump speed is 20rmp, the single residence time of the solution is 25s, and the solution flow rate is 10mL/min. Cycled 8 times under the conditions of no catalyst and optical power density of 50mW/cm ² , as can be seen from Figure 1, the antibiotic ofloxacin hardly degrades.

Embodiment 2: Bismuth tungstate photocatalytically treats the antibiotic ofloxacin (OFX) at different flow rates

Weigh the catalyst bismuth tungstate and disperse it in the antibiotic ofloxacin (6mg/L) solution, absorb it in the dark for 1h to reach the adsorption-desorption equilibrium, use a peristaltic pump to pass the solution into the continuous flow reactor, and carry out the photocatalytic reaction under the xenon lamp , the solution after the reaction was passed into the beaker, the solution was sampled after the single reaction, and the solution was re-passed into the continuous flow reactor for the next light reaction. After the sampled solution was filtered through a 0.22 μm filter membrane, UV-Vis spectroscopy was used The absorbance of OFX (290 nm) was measured with a photometer. When the peristaltic pump speed is 10, 20, 40rmp, the single residence time of the solution is 50, 25, 13s, and the solution flow rate is 5, 10, 20mL/min. Cycle 5 times under the conditions of optical power density 50mW/cm ² and catalyst concentration 1g/L. The experimental results are shown in Figure 2. The degradation effect decreases with the increase of the solution flow rate. When the flow rate is large, the solution flows quickly and causes The short residence time reduces the degradation effect. When the flow rate is small, the solution flow is slow and the residence time is long. The degradation effect is good, but the catalyst will be deposited. Choose 10mL/min for the experiment. There is a certain degradation effect and the flow rate is larger and the time consumption is shorter.

Embodiment 3: Bismuth tungstate photocatalytically treats antibiotic ofloxacin (OFX) under different catalyst concentrations

Weigh the catalyst bismuth tungstate and disperse it in the antibiotic ofloxacin (6mg/L) solution, absorb it in the dark for 1h to reach the adsorption-desorption equilibrium, use a peristaltic pump to pass the solution into the continuous flow reactor, and carry out the photocatalytic reaction under the xenon lamp , the solution after the reaction was passed into the beaker, the solution was sampled after the single reaction, and the solution was re-passed into the continuous flow reactor for the next light reaction. After the sampled solution was filtered through a 0.22 μm filter membrane, UV-Vis spectroscopy was used The absorbance of OFX (290 nm) was measured with a photometer. The solution was circulated 5 times under the conditions of peristaltic pump speed of 20rmp, optical power density of 50mW/cm ² , and catalyst concentration of 0.5, 1, and 1.5g/L. The experimental results are shown in Figure 3. The degradation effect increases with the increase of catalyst concentration And enhancement, when the catalyst concentration is 1.5g/L, the degradation effect is not greatly improved compared with 1.0g/L, and too much catalyst amount will lead to waste, so the catalyst concentration is selected to be 1g/L for experiment.

Embodiment 4: The antibiotic ofloxacin (OFX) of different concentrations is treated with bismuth tungstate photocatalytically

Weigh the catalyst bismuth tungstate and disperse it in the antibiotic ofloxacin solution, absorb it in the dark for 1 hour to reach the adsorption-desorption equilibrium, use a peristaltic pump to pass the solution into a continuous flow reactor, and carry out photocatalytic reaction under a xenon lamp, and the reacted solution After the single reaction, the solution was sampled, and the solution was reintroduced into the continuous flow reactor for the next light reaction. After the sampled solution was filtered through a 0.22 μm filter membrane, the UV-Vis spectrophotometer was used to measure OFX ( 290nm) absorbance. The solution was circulated 5 times under the conditions of peristaltic pump speed of 20rmp, optical power density of 50mW/cm ² , and antibiotic concentration of 6, 9, and 12mg/L. The experimental results are shown in Figure 4. Bismuth tungstate is suitable for degrading ofloxacin solutions of different concentrations. When the antibiotic concentration is 6mg/L, the removal rate reaches 90% after 5 cycles. In order to enhance the degradation effect of antibiotics, the light channel can be extended The length, increase the optical power density, increase the number of cycles and other methods to achieve.

The research shows that this equipment can efficiently treat antibiotic wastewater under suitable conditions.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A continuous flow reactor for photocatalytic treatment of antibiotic waste water, characterized in that it comprises: Magnetic stirring device, peristaltic pump, light source, continuous flow reactor, collection device; The magnetic stirring device is sequentially connected with a peristaltic pump, a continuous flow reactor, and a collection device, and a light source is arranged above the continuous flow reactor; The antibiotic wastewater containing the catalyst reaches the adsorption-desorption equilibrium in the magnetic stirring device; The single residence time of the antibiotic wastewater containing the catalyst in the continuous flow reactor is 5-300s. 2. The continuous flow reaction device for photocatalytic treatment of antibiotic wastewater according to claim 1, wherein the continuous flow reactor is an S-shaped channel and is made of a transparent material. 3. The continuous flow reaction device for photocatalytic treatment of antibiotic wastewater according to claim 1, wherein the continuous flow reactor channel is millimeter in size, 1.1 to 1.2 m long, 2 to 2.4 mm wide, and 2 to 2.4 mm high. . 4. The continuous flow reaction device for photocatalytic treatment of antibiotic wastewater according to claim 1, wherein the magnetic stirring device comprises: a container and a stirring device. 5. The continuous flow reaction device for photocatalytic treatment of antibiotic waste water as claimed in claim 1, characterized in that, each device is connected with a silicone tube. 6. A method for the treatment of antibiotic waste water by a continuous flow reactor, characterized in that it comprises: Disperse the catalyst in the antibiotic wastewater, and then stir it to make it reach the adsorption-desorption equilibrium; Pumping the wastewater that has reached the adsorption-desorption balance into a continuous flow reaction device, and performing a photocatalytic reaction under light; The solution after the reaction is collected, and re-introduced into the device for cyclic reaction to obtain the obtained product. 7. The method for treating antibiotic waste water with continuous flow reaction device as claimed in claim 6, characterized in that, the solution flow rate is 0.1-50mL/min. 8. the method for continuous flow reactor treatment antibiotic wastewater as claimed in claim 6, is characterized in that, described antibiotic wastewater is quinolones, sulfonamides, tetracyclines, β-lactams, macrolides, cephalosporins One of mycocins, aminoglycosides, and lincosamides. 9. the method for the continuous flow reactor treatment antibiotic wastewater as claimed in claim 6, is characterized in that, described catalyst is bismuth tungstate, titanium dioxide, titanium silicon molecular sieve, carbon nitride, zinc oxide, bismuth oxide, tin oxide, Cadmium sulfide and one or more of metal doping, material loading and reduction modification materials. 10. Application of the device according to any one of claims 1-5 in the field of water treatment.

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