CN114588855A - Method for regulating and controlling catalyst activity by using continuous flow photocatalytic reaction device and application thereof - Google Patents
Method for regulating and controlling catalyst activity by using continuous flow photocatalytic reaction device and application thereof Download PDFInfo
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- CN114588855A CN114588855A CN202210085323.XA CN202210085323A CN114588855A CN 114588855 A CN114588855 A CN 114588855A CN 202210085323 A CN202210085323 A CN 202210085323A CN 114588855 A CN114588855 A CN 114588855A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
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- B01J19/0053—Details of the reactor
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B01J2219/00164—Controlling or regulating processes controlling the flow
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- C02F2201/32—Details relating to UV-irradiation devices
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- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to the technical field of photocatalytic oxidation, and discloses a method for regulating and controlling catalyst activity by using a continuous flow photocatalytic reaction device and application thereof. The method comprises the steps of placing a diluent of a target pollutant into a liquid storage tank, and tightly connecting the liquid storage tank with a photocatalytic reactor through a silicone tube; controlling the water inflow flow rate to be 5-30 mL/min and the water outflow flow rate to be 1-15 mL/min respectively through a single-channel peristaltic pump, ensuring that the average water flow rate is 3-20 mL/min, operating the device in a continuous flow state, and continuously exciting the catalyst by ultraviolet light until the target pollutants are completely oxidized. The method changes the contact time of the target object and the catalyst by adjusting the flow rate of the fluid to be treated at the water inlet and the water outlet under the condition of ensuring high-efficiency treatment of the target object, thereby regulating and controlling the activity and the service life of the catalyst. Can be used for the research of related mechanisms such as catalyst inactivation and the like, and the fields of medical wastewater treatment, secondary effluent of sewage treatment or deep purification of urban drinking water and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalytic oxidation, and particularly relates to a method for regulating and controlling catalyst activity by using a continuous flow photocatalytic reaction device and application thereof.
Background
Photocatalysis is based on the generation of active species with redox ability by semiconductor photocatalysts under ultraviolet irradiation to purify pollutants. The photocatalytic purification technology for removing organic pollutants in water has the following advantages: 1) The reaction conditions are mild: the semiconductor can generate a large amount of reactive species under the normal temperature and pressure by light excitation; 2) high removal efficiency and strong detoxification capability: the original structure of the organic pollutants is quickly destroyed and gradually converted into micromolecular and low-toxicity products, and even the products are completely mineralized, so that the purification effect is good; 3) the commercial semiconductor catalyst has stable property, wide source, low cost and longer service life; 4) in the future, the sunlight is expected to be used as an excitation light source, so that the processing cost is greatly reduced; the technology shows great application potential in the aspect of deep purification of water bodies. However, the following limitations have been studied: the light source intensity and the operation quantity can not be flexibly adjusted according to the actual water quantity and the water quality of the water body to be treated, and energy is wasted; the powder photocatalyst is difficult to recover and is discharged into water body to cause secondary pollution; the fixed photocatalyst has small loading capacity and poor fixing effect; the difference between the static photocatalytic reaction and the actual treatment condition is large, and the research result is not easy to be converted into the operation condition of the actual water treatment process. Therefore, the development of a continuous flow type fixed bed photocatalytic reactor capable of flexibly controlling a plurality of groups of light sources is a necessary choice for researching a fixed photocatalyst inactivation mechanism and applying a photocatalytic technology to an actual water treatment process.
Disclosure of Invention
In order to solve the problems in the prior art, the present invention provides a method for controlling the activity of a catalyst by using a continuous flow photocatalytic reaction apparatus. The method utilizes the continuous flow photocatalytic reaction device, can flexibly adjust the intensity of a light source according to the actual water quantity and water quality conditions of the water body to be treated, and is implemented by energy-saving continuous flow photocatalytic reaction with higher purification efficiency.
The invention also aims to provide the energy-saving continuous-flow photocatalytic reaction device.
The invention also aims to provide the application of the energy-saving continuous flow photocatalytic reaction device in the fields of medical wastewater treatment, secondary effluent of municipal sewage treatment plants or municipal drinking water deep purification.
The purpose of the invention is realized by the following technical scheme:
a method for regulating and controlling the activity of a catalyst by using a continuous flow photocatalytic reaction device comprises the following specific steps:
s1, uniformly coating a catalyst suspension on a catalyst carrier, drying and fixing, calcining the carrier attached with the photocatalyst at 150-400 ℃ to prepare the photocatalyst, and combining the photocatalyst with a fixing frame to prepare a photocatalyst component;
s2, placing a diluent of a target pollutant in a liquid storage tank of the continuous flow photocatalytic reaction device, tightly connecting the liquid storage tank with the photocatalytic reactor through a silicone tube, respectively controlling the water inlet flow rate of the photocatalytic reactor to be 3-30 mL/min and the water outlet flow rate of the photocatalytic reactor to be 1-20 mL/min through a single-channel peristaltic pump, ensuring that the average water flow rate is 3-20 mL/min, operating the device in a continuous flow state, and changing the contact time between water flow and a fixed photocatalyst by controlling the flow rate of the water flow at the water inlet and the water outlet of the device to realize the regulation and control of the activity of the catalyst.
Preferably, the catalyst suspension in step S1 is TiO2Solutions, ZnO solutions or Pd @ TiO2More than one of the solutions, the concentration of the catalyst suspension is 0.02-2 g/mL, and the catalyst carrier is foamed nickel,More than one of foamed aluminum and a glass fiber membrane, wherein the calcining time is 4-8 h.
Preferably, the concentration of the diluent of the target pollutant in the step S2 is 5-40 mg/L, the target pollutant is 5-fluorouracil, the treatment time is 3-8 h, and the irradiation wavelength of the ultraviolet lamp is 320-410 nm.
The method realizes a continuous flow photocatalytic reaction device for regulating and controlling the activity of a catalyst, and the photocatalytic reaction device comprises a photocatalytic reactor, a liquid storage tank and a single-channel peristaltic pump; the liquid storage tank is connected with the photocatalytic reactor through a silicone tube, and the single-channel peristaltic pump is arranged on the silicone tube and is used for controlling the flow of the fluid to be treated at the water inlet and the water outlet of the reactor; a photocatalyst component and an ultraviolet lamp set are arranged in the photocatalytic reactor; the photocatalyst component and the ultraviolet lamp group are fixed on different side surfaces of the photocatalytic reactor in a crossed manner and keep an interval with the other side surface; the photocatalyst components are arranged on two sides of the ultraviolet lamp groups in parallel at intervals, and the photocatalyst components and the adjacent ultraviolet lamp groups form a snake-shaped water flow channel.
Further, the photocatalyst component comprises a fixing frame and a photocatalyst net, wherein the fixing frame is a frame with a hollow center, and the photocatalyst net is fixed in the middle of the fixing frame.
Furthermore, the shell of the photocatalytic reactor is made of a corrosion-resistant hard material; the photocatalysis net is a dense porous metal net material.
Further, the liquid storage pot includes first liquid storage pot and second liquid storage pot, first liquid storage pot is equipped with the delivery outlet, the second liquid storage pot is equipped with the input port, delivery outlet and input port respectively through the silicone tube with the photocatalytic reactor is connected.
Furthermore, the ultraviolet lamp set comprises a plurality of ultraviolet lamp tubes, the ultraviolet lamp tubes are connected in parallel through a circuit, a protective cover is arranged outside the ultraviolet lamp set, a plurality of baffle plates are arranged in the protective cover at equal intervals, and the ultraviolet lamp tubes are arranged between the baffle plates and used for supporting and isolating the ultraviolet lamp tubes.
Furthermore, the photocatalytic reactor is also provided with a water inlet and a water outlet; the single-channel peristaltic pump comprises a first single-channel peristaltic pump and a second single-channel peristaltic pump, wherein the first single-channel peristaltic pump controls the flow of the water inlet to be larger than the flow of the water outlet of the second single-channel peristaltic pump.
The continuous flow photocatalytic reaction device is applied to the fields of medical wastewater treatment, secondary effluent of sewage treatment or deep purification of urban drinking water.
The hydraulic retention time of the present invention refers to the time from the moment when the reaction solution enters to the moment when the reaction solution flows out of the reactor, and the hydraulic retention time is equal to the constant water storage amount (mL) of the reactor)/(inflow flow rate-outflow flow rate of the reactor); as long as fresh solution to be treated continuously flows in and treated solution flows out of the reactor, the solution to be treated does not always stay at a certain position in the reactor, the solution which flows into the reactor earlier contacts with the catalyst firstly and flows forwards slowly in the reactor, the total stay time is 60-360 min, the catalyst is excited by ultraviolet light during the hydraulic stay time, hydroxyl free radicals with strong oxidation are continuously generated, the free radicals are transferred from the surface of the catalyst to bulk phase solution to participate in the oxidative degradation of a dominant target, and the system realizes the effective removal of the target pollutant by means of the strong oxidation of the free radicals and the long-term hydraulic stay of the solution in the reactor.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention relates to a method for regulating and controlling the activity of a catalyst by utilizing a continuous flow photocatalytic reaction device, which changes the contact time of target 5-fluorouracil and the catalyst by regulating the flow speed of fluid to be treated at a water inlet and a water outlet of a reactor under the condition of ensuring that the treatment efficiency of the target 5-fluorouracil is basically unchanged, thereby achieving the purpose of regulating and controlling the activity of the catalyst. In the method, the removal rate of the target pollutant 5-fluorouracil can reach more than 80% after 6 hours of ultraviolet irradiation, the reaction time is continuously prolonged, and the removal efficiency of the target pollutant 5-fluorouracil can be increased to more than 90%. In addition, when the flow rate of the fluid to be treated is increased from 5mL/min to 15mL/min, after 120h of continuous experiments, the reduction ratio of the activity of the catalyst is reduced from 64% to below 20%, which shows that the activity of the catalyst after long-time operation can be regulated and controlled by regulating the flow rate of the fluid to be treated. The method has simple principle and operation, and is easy to realize flexible regulation and control of the catalyst activity.
2. The photocatalytic reaction device can realize independent control among all light sources, and all ultraviolet lamp tubes are connected in parallel, so that the device is efficient and energy-saving, and can flexibly adjust the intensity and the position of the light sources. The ultraviolet lamp tubes with different numbers and different positions can be selectively opened in three different water using periods of high, medium and low in one day, so that flexible control and accurate utilization of a light source can be realized, and energy is saved.
3. The continuous flow photocatalytic reactor has compact structure and small occupied area, adopts the snakelike water flow channel, prolongs the hydraulic retention time of fluid to be treated while controlling the length of the reactor, meets the requirement of high-efficiency treatment of wastewater, and is particularly suitable for deep oxidation of refractory organic matters in secondary effluent of a sewage treatment plant or urban drinking water.
4. The photocatalytic reaction device can delay the inactivation of the catalyst, simplify the operation process and reduce the maintenance cost of the device by reasonably regulating the flow rate of inlet/outlet water.
Drawings
FIG. 1 is a structural diagram of an energy-efficient continuous-flow photocatalytic reaction apparatus according to the present invention.
FIG. 2 is a plan view of the photocatalytic reaction apparatus according to the present invention.
FIG. 3 is a front view, a side view and a rear view of a photocatalyst module inside the photocatalytic reaction device according to the present invention.
FIG. 4 is a graph showing the change of the degradation proportion of 5-fluorouracil, a target pollutant in water, in application examples 1-3, with time through adsorption, photodegradation and photocatalysis.
FIG. 5 is a comparison graph of the photocatalytic degradation efficiency change of the target pollutant 5-fluorouracil before and after 120h continuous experiments under different inlet/outlet water flow rates in application examples 3-6.
Detailed Description
The present invention will be further described with reference to the following specific examples. But should not be construed as limiting the 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.
Example 1
FIG. 1 is a structural diagram of an efficient energy-saving continuous flow photocatalytic reaction device according to the present invention. FIG. 2 is a top view of the photocatalytic reaction device according to the present invention. As shown in fig. 1 and fig. 2, an efficient energy-saving continuous flow photocatalytic reaction device comprises a photocatalytic reactor 1, a liquid storage tank 2 and a single-channel peristaltic pump 3; the liquid storage tank 2 is connected with the photocatalytic reactor 1 through a silicone tube 4, and the single-channel peristaltic pump is arranged on the silicone tube and is used for controlling the flow of the fluid to be treated at the water inlet and the water outlet of the reactor; a photocatalyst component 11 and an ultraviolet lamp group 12 are arranged in the photocatalytic reactor 1; the photocatalyst component 11 and the ultraviolet lamp group 12 are fixed on different side surfaces of the photocatalytic reactor 1 in a crossed manner, and the distance between the photocatalyst component and the other side surface is 1-3 cm; the photocatalyst component 11 is fixed on the side surface of the photocatalytic reactor 1 through a square slot and is used for photocatalytic oxidation of target pollutants. The square slot is about 2mm wide and 3mm deep groove arranged on the inner side wall and the bottom of the reactor, so that the fixing frame of the catalyst component is conveniently inserted into the groove, and the component can be vertically fixed in the reactor and is convenient to take and mount. The distance that photocatalyst component 11 is parallel and spaced is 2 ~ 5cm and sets up the both sides of ultraviolet banks 12, photocatalyst component 11 and adjacent ultraviolet banks 12 form snakelike rivers passageway.
As shown in fig. 3, the photocatalyst module 11 includes a fixing frame 111 and a photocatalyst net 112, the fixing frame 111 is a frame with two different sizes and a hollow center, and the photocatalyst net 112 is fixed at the middle position of the fixing frame 111 by screws and nuts. The size of the photocatalytic net 112 is 85 × 100 × 1.0mm, and the area of length × width occupies 100% of the hollowed-out portion of the fixed frame 111. The photocatalysis net is a dense porous metal net material (such as foamed nickel and foamed aluminum), and the surface of the photocatalysis net is attached with a photocatalyst. The compact porous structure can increase the fixed amount of the photocatalyst and improve the fixing effect. The photocatalyst is a semi-photocatalystThe conductive metal oxide or its modified material may be TiO2、ZnO、Pd@TiO2、CeO2And the like.
The shell of the photocatalytic reactor is made of corrosion-resistant hard materials, such as organic glass, glass or stainless steel.
The liquid storage tank 2 comprises a first liquid storage tank 21 and a second liquid storage tank 22, wherein the first liquid storage tank 21 is provided with an output port 211, the second liquid storage tank 22 is provided with an input port 221, and the output port and the input port are respectively connected with the photocatalytic reactor through silicone tubes. The liquid storage tank 2 is used for containing fluid to be treated and treated liquid discharged from the reactor. The fluid to be treated is an aqueous solution of a single target medicament, wherein the mass concentration of the target medicament is 20mg/L, and the medicament is purchased from Shanghai Aladdin Biotechnology GmbH.
The ultraviolet lamp set 12 comprises a plurality of ultraviolet lamp tubes 120, the ultraviolet lamp tubes 120 are connected in parallel by a circuit, the parallel circuit can control the ultraviolet lamp tubes 120 at different positions and the actual operation number thereof, and the ultraviolet lamp tubes 120 and the actual operation number thereof are adjusted to the optimal light source position and light source intensity respectively at the peak and the low peak of water flow and under the conditions that the inlet water is high in organic load and low in load, so that the light source utilization rate is effectively improved, and the energy is saved. The outer portion of the ultraviolet lamp group 12 is provided with a protective cover 121, the protective cover 121 is a hollow closed structure, a plurality of baffles 122 are arranged in the protective cover 121 at equal intervals, and the ultraviolet lamp tubes 120 are transversely arranged between the baffles 122 and used for supporting and isolating the ultraviolet lamp tubes. So that the immobilized photocatalyst in contact with the fluid to be treated can receive maximum illumination and avoid the possible danger of the uv lamp circuit coming into contact with water. The material of the protection cover 121 is transparent organic glass, and the purpose is to enable the ultraviolet light transmittance to reach more than 90%. The power consumption of the ultraviolet lamp tube 120 is 5W/piece, and the light intensity of the fixed photocatalyst surface is 33-68 mW/cm2。
The photocatalytic reactor 1 is also provided with a water inlet 13 and a water outlet 14, wherein the distance between the water inlet 13 and the bottom of the reactor is 2-4 cm, the distance between the water outlet 14 and the bottom of the reactor is 1-3 cm, and the diameters of the water inlet and the water outlet are 3.2-5.0 mm; single channel peristaltic pump 3 includes first single channel peristaltic pump 31 and second single channel peristaltic pump 32, the flow of first single channel peristaltic pump 31 control water inlet is 3 ~ 30mL/min, the flow of second single channel peristaltic pump 32 control delivery port is 1 ~ 20mL/min, the inflow is greater than the outflow, thereby guarantees there is certain water storage volume in the reaction vessel, and the purpose makes the abundant contact of target and catalyst and takes place the reaction.
Application example 1
The energy-saving continuous flow photocatalytic reaction device in the embodiment 1 is used for adsorbing and removing target pollutants in a water body, and comprises the following steps:
(1) preparation of a fixed photocatalyst: 10mL of TiO with the concentration of 0.02g/mL which is uniformly dispersed2The suspension was applied uniformly to 85X 100X 1.0mm foamed nickel with a pore size of 0.2mm and dried immediately to fix the TiO2More stably attaching, placing the reticular foam nickel in a muffle furnace to calcine for 7h at 250 ℃ to prepare the foam nickel loaded TiO2Photocatalytic network 112.
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) Adsorbing and removing target pollutants: the first liquid storage tank 21 is connected with the photocatalytic reactor 1 through a silicone tube 4, two single-channel peristaltic pumps 31 and 32 which are respectively close to a water inlet and a water outlet are opened to respectively control the water inlet flow rate and the water outlet flow rate of the photocatalytic reactor to be 7mL/min and 2mL/min respectively, and the treatment time is 6 hours. Under the condition, the water storage amount in the photocatalytic reactor is 1800mL, the liquid level height is 4.4cm, an ultraviolet lamp does not need to be turned on, the reactor is in a completely dark environment by adopting a light shield, and the device continuously operates in a continuous flowing state.
During the experiment, samples are manually taken from the second liquid storage tank 22 connected with the water outlet at specific time intervals, the content of the target substance 5-fluorouracil in water is analyzed and determined, and a curve with a circular symbol in fig. 4 is a graph of the adsorption removal efficiency-time change of the target pollutant 5-fluorouracil in application example 1 (control group 1). From trial to trialThe experimental result shows that the removal efficiency of the target pollutant 5-fluorouracil is almost unchanged along with the prolonging of the treatment time, which indicates that the substance belongs to a strong polar compound and is not easy to be adsorbed on TiO2The surface of the catalyst. The application example can be used for removing nonpolar or weakly polar pollutants in water by an adsorption method, wherein the removal effect is related to the polarity and the adsorbability of the pollutants.
Application example 2
The energy-saving continuous flow photocatalytic reaction device in the embodiment 1 is used for removing target pollutants in a water body through photodegradation, and comprises the following steps:
(1) preparation of a blank fixed catalyst: taking hollow foam nickel with the diameter of 85 multiplied by 100 multiplied by 1.0mm and the aperture of 0.2mm, fixing the hollow foam nickel in two fixing frames of the photocatalyst component 11 through 4 groups of screws and nuts to obtain fixed TiO2Replacement assembly of photocatalyst (blank).
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) Degrading target pollutants by continuous flowing light: the first liquid storage tank 21 is connected with the photocatalytic reactor 1 through a silicone tube 4, two single-channel peristaltic pumps 31 and 32 which are respectively close to a water inlet and a water outlet are opened to respectively control the water inlet flow rate and the water outlet flow rate of the photocatalytic reactor to be 7mL/min and 2mL/min respectively, and the treatment time is 6 hours. Under the condition, the water storage amount in the photocatalytic reactor is 1800mL, the liquid level height is 4.4cm, the requirements of the illumination range and the illumination intensity can be met only by opening 3 ultraviolet lamps (with the wavelength of 365nm) close to the bottom, the device operates in a continuous flowing state, and the target pollutant 5-fluorouracil in the fluid to be treated is continuously illuminated and gradually decomposed.
During the experiment, samples were manually taken from the second reservoir 22 connected to the water outlet at specific time intervals, and the content of the target 5-fluorouracil in the water was analyzed and measured, and the curve with a square symbol in fig. 4 is a graph of the photodegradation removal efficiency of the target contaminant in application example 2 versus the time (control 2). From the test results, the removal efficiency of the target contaminant 5-fluorouracil hardly changes with the increase of the treatment time, which indicates that the substance cannot absorb ultraviolet light with the wavelength of 365nm, and the characteristic absorption wavelength of the substance is related to the substance structure and the type of functional group. The application example can be used for removing target pollutants in water by photodegradation, wherein the photodegradation removal effect is related to the light absorption characteristics of the pollutants.
Application example 3
The energy-saving continuous flow photocatalytic reaction device in the embodiment 1 is used for photocatalytic degradation of target pollutants in water, and comprises the following steps:
(1) preparation of a fixed photocatalyst: 10mL of TiO with the concentration of 0.02g/mL which is uniformly dispersed2The suspension was applied uniformly to 85X 100X 1.0mm foamed nickel with a pore size of 0.2mm and dried immediately to fix the TiO2More stably attaching, placing the reticular foam nickel in a muffle furnace to calcine for 7h at 250 ℃ to prepare the foam nickel loaded TiO2Photocatalytic network 112.
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) And (3) removing target pollutants by continuous flow photocatalysis: the first liquid storage tank 21 is connected with the photocatalytic reactor 1 through a silicone tube 4, two single-channel peristaltic pumps 31 and 32 which are respectively close to a water inlet and a water outlet are opened to respectively control the water inlet flow rate and the water outlet flow rate of the photocatalytic reactor to be 7mL/min and 2mL/min respectively, and the treatment time is 6 hours. Under the condition, the water storage amount in the photocatalytic reactor is 1800mL, the liquid level height is 4.4cm, the requirements of illumination range and intensity can be met only by opening 3 ultraviolet lamps close to the bottom, the device operates in a continuous flowing state, and TiO is fixed 2The photocatalyst is excited under the irradiation of an ultraviolet lamp, and the target pollutant 5-fluorouracil in the fluid to be treated is gradually oxidized until most harmful substances in the water are removed.
During the experiment, samples are manually taken from the second liquid storage tank 22 connected with the water outlet at specific time intervals, the content of the target 5-fluorouracil in water is analyzed and determined, and a curve marked with a triangle in fig. 4 is a graph (experimental group) of the photocatalytic degradation efficiency-time change of the target pollutant in the application example 3. According to test results, the removal rate of the target pollutant 5-fluorouracil in the application example can reach more than 80% after 6 hours of ultraviolet irradiation, the reaction time is continuously prolonged, and the removal efficiency of the target pollutant 5-fluorouracil can be increased to more than 90%. The energy-saving continuous flow photocatalytic reaction device can be used for pretreatment of medical wastewater, deep purification of secondary effluent or drinking water of urban sewage treatment plants and the like.
Application example 4
The energy-saving continuous flow photocatalytic reaction device in the embodiment 1 is used for photocatalytic degradation of target pollutants in water, and comprises the following steps:
(1) preparation of a fixed photocatalyst: and (3) uniformly coating 10mL of ZnO suspension with the concentration of 0.02g/mL which is uniformly dispersed on foamed nickel with the aperture of 0.2mm and the thickness of 85X 100X 1.0mm, immediately drying and fixing, and calcining the reticulated foamed nickel in a muffle furnace at 250 ℃ for 7 hours to obtain the foamed nickel loaded ZnO photocatalytic network 112 in order to ensure that ZnO is more stably attached.
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) And (3) removing target pollutants by continuous flow photocatalysis: the first liquid storage tank 21 is connected with the photocatalytic reactor 1 through a silicone tube 4, two single-channel peristaltic pumps 31 and 32 which are respectively close to the water inlet and the water outlet are opened to respectively control the water inlet flow rate and the water outlet flow rate of the photocatalytic reactor 1 to be 7mL/min and 2mL/min respectively, and the treatment time is 6 hours. Under the condition, the water storage amount in the photocatalytic reactor is 1800mL, the liquid level height is 4.4cm, the requirements of illumination range and intensity can be met only by opening 3 ultraviolet lamps close to the bottom, the device operates in a continuous flowing state, the fixed ZnO photocatalyst is excited under the irradiation of the ultraviolet lamps, and the target pollutant 5-fluorouracil in the fluid to be treated is gradually oxidized until most harmful substances in the water are removed.
Application example 5
The energy-saving continuous flow photocatalytic reaction device in the embodiment 1 is used for photocatalytic degradation of target pollutants in water, and comprises the following steps:
(1) preparation of a fixed photocatalyst: taking 10mL of uniformly dispersed Pd @ TiO with the concentration of 0.02g/mL 2The suspension was uniformly coated on a glass fiber membrane of 85X 100X 0.8mm, pore size 4X 4mm, and immediately dried to fix Pd @ TiO2More stably attaching, placing the glass fiber membrane in a muffle furnace to be calcined for 7h at 250 ℃ to prepare the glass fiber membrane loaded Pd @ TiO2Photocatalytic network 112.
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) And (3) removing target pollutants by continuous flow photocatalysis: the first liquid storage tank 21 is connected with the photocatalytic reactor 1 through a silicone tube 4, 2 single-channel peristaltic pumps 31 and 32 close to the water inlet and the water outlet respectively are opened to control the flow rates of water inlet and outlet to be 7mL/min and 2mL/min respectively, and the treatment time is 6 hours. Under the condition, the water storage amount in the photocatalytic reactor is 1800mL, the liquid level height is 4.4cm, the requirements of illumination range and intensity can be met only by opening 3 ultraviolet lamps close to the bottom, the device operates in a continuous flowing state, and Pd @ TiO is fixed2The photocatalyst is excited under the irradiation of an ultraviolet lamp, and the target pollutant 5-fluorouracil in the fluid to be treated is gradually oxidized until most harmful substances in water are removed.
Application example 6
The energy-saving continuous flow photocatalytic reactor of example 1 was used to carry out a stability test experiment for long-term recycle of catalyst, comprising the following steps:
(1) preparation of a fixed photocatalyst: 10mL of TiO with the concentration of 0.02g/mL which is uniformly dispersed2The suspension was applied uniformly to 85X 100X 1.0mm foamed nickel with a pore size of 0.2mm and dried immediately to fix the TiO2More stably attaching, and calcining the reticular foamed nickel in a muffle furnace at 250 ℃ for 7h to prepare the foamed nickel loaded TiO2Photocatalytic network 112.
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) And (3) continuously using the catalyst for more than 120h to test the stability: the first liquid storage tank 21 is connected with the photocatalytic reactor 1 through a silicone tube 4, 2 single-channel peristaltic pumps 31 and 32 close to a water inlet and a water outlet respectively are opened to control the flow rates of water inlet and outlet to be 7mL/min and 2mL/min respectively, and the single treatment time is 6 hours. Under the condition, the water storage amount in the photocatalytic reactor 1 is 1800mL, the liquid level height is 4.4cm, and only 3 ultraviolet lamps close to the bottom are started; and (3) keeping the flow rate of the inlet water and the outlet water all the time, continuously monitoring for 120h, and evaluating the activity change condition of the catalyst under the condition of the flow rate of the inlet water according to the removal efficiency of the target pollutants.
During the test, samples are manually taken from the second liquid storage tank 22 connected with the water outlet at specific time intervals, and the content of the target object in the water is analyzed and determined. FIG. 5 is a comparison graph of the photocatalytic degradation efficiency change of the target pollutant 5-fluorouracil before and after 120h continuous experiments under different inlet/outlet water flow rates in application examples 3-6. The bar graph filled with diagonal line-shaped shading is the photocatalytic removal efficiency of 5-fluorouracil after 120 hours of continuous operation in application example 4. The test result shows that the application example continuously runs for 120 hours, the removal rate of 5-fluorouracil is reduced to 20%, and the activity of the catalyst is obviously reduced. The energy-saving continuous flow photocatalytic reaction device can be used for researching the inactivation mechanism of the fixed photocatalyst.
Application example 7
The energy-saving continuous flow photocatalytic reaction device in the embodiment 1 is used for photocatalytic degradation of target pollutants in water, and comprises the following steps:
(1) preparation of a fixed photocatalyst: 10mL of TiO with the concentration of 0.02g/mL which is uniformly dispersed2The suspension was applied uniformly to 85X 100X 1.0mm foamed nickel with a pore size of 0.2mm and dried immediately to fix the TiO2More stably attaching, and calcining the reticular foamed nickel in a muffle furnace at 250 ℃ for 7h to prepare the foamed nickel loaded TiO 2Photocatalytic network 112.
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) And (3) removing target pollutants by continuous flow photocatalysis: the first liquid storage tank 21 is connected with the photocatalytic reactor through a silicone tube 4, two single-channel peristaltic pumps 31 and 32 which are respectively close to the water inlet and the water outlet are opened to respectively control the flow rates of water inlet and outlet to be 25mL/min and 10mL/min, and the treatment time is 6 hours. Under the condition, the water storage volume in the reaction container is 5400mL, the liquid level height is 13.2cm, the requirements of illumination range and intensity can be met by opening 6 ultraviolet lamps at the middle part and the bottom part, the device operates in a continuous flowing state, and TiO is fixed2The photocatalyst is excited under the irradiation of the ultraviolet lamp, and the target pollutant in the fluid to be treated is gradually oxidized until most harmful substances in the water are removed.
During the test, samples are manually taken from the second liquid storage tank 22 connected with the water outlet at specific time intervals, and the content of the target object in the water is analyzed and determined. The bar graph with the filled parts being dense points in fig. 5 is the removal efficiency of the target pollutant 5-fluorouracil in application example 5 after 6h of light treatment. The test result shows that the removal rate of the 5-fluorouracil in the application example can reach more than 85% after 6 hours of ultraviolet irradiation, and the pollutant purification effect is ideal.
Application example 8
The energy-saving continuous flow photocatalytic reaction device in the embodiment 1 is used for carrying out a stability test experiment of long-term recycling of the catalyst, and comprises the following steps:
(1) preparation of a fixed photocatalyst: 10mL of TiO with the concentration of 0.02g/mL which is uniformly dispersed2The suspension was applied uniformly to 85X 100X 1.0mm foamed nickel with a pore size of 0.2mm and dried immediately to fix the TiO2More stably attaching, and calcining the reticular foamed nickel in a muffle furnace at 250 ℃ for 7h to prepare the foamed nickel loaded TiO2Photocatalytic network 112.
(2) Preparing a solution to be treated: 10mL of 1000ppm 5-fluorouracil concentrated standard solution prepared in advance is diluted to 20ppm in a 1000mL brown volumetric flask, and a plurality of bottles are prepared and placed in a first liquid storage tank 21.
(3) And (3) continuously using the catalyst for more than 120h to test the stability: the first liquid storage tank 21 is connected with the photocatalytic reactor 1 through a silicone tube 4, two single-channel peristaltic pumps 31 and 32 which are respectively close to a water inlet and a water outlet are opened to respectively control the flow rates of water inlet and outlet to be 25mL/min and 10mL/min, and the single treatment time is 6 hours. Under the condition, the water storage amount in the photocatalytic reactor 1 is 5400mL, the liquid level height is 13.2cm, and 6 ultraviolet lamps at the middle part and the bottom part are started to meet the requirements of illumination range and intensity; and (3) keeping the flow rate of the inlet water and the outlet water all the time, continuously monitoring for 120h, and evaluating the activity change condition of the catalyst under the condition of the flow rate of the inlet water according to the removal efficiency of the target pollutants.
During the test, samples are manually taken from the second liquid storage tank 22 connected with the water outlet at specific time intervals, and the content of the target substance 5-fluorouracil in water is analyzed and determined. FIG. 5 is a comparison graph of the change of photocatalytic degradation efficiency of 5-fluorouracil before and after 120h continuous experiments under different water inlet/outlet flow rates in application examples 3-6. The bar graph filled with diagonal line-shaped shading in fig. 5 shows the photocatalytic removal efficiency of the target contaminant 5-fluorouracil after 120 hours of continuous operation in application example 6. According to test results, the application example continuously runs for 120 hours, the removal rate of the target pollutant 5-fluorouracil is 73%, and the activity of the catalyst is reduced by less than 10%. The energy-saving continuous flow photocatalytic reaction device accelerates the flow velocity of water passing on the surface of the catalyst by increasing the flow velocity of water inlet and water outlet, thereby inhibiting the adsorption and accumulation of pollutants on the surface of the catalyst, slowing down the inactivation speed of the fixed photocatalyst, prolonging the service life of the catalyst and being beneficial to reducing the maintenance cost of a reactor.
The continuous flow energy-saving photocatalytic reaction device provided by the invention has the advantages of compact structure and small occupied area, and can effectively reduce the processing cost; the running number of the lamp tubes can be adjusted according to the actual water quantity and water quality requirements, so that the energy is effectively saved; the fixed photocatalyst is prepared from a compact porous metal material, so that the problem that a powder catalyst is difficult to recover is solved, the fixed amount of the catalyst on the surface of the porous material is large, the fixed effect is good, the hydraulic retention time of a fluid to be treated can be prolonged under the condition of not increasing the length of a reactor by adopting the design of a snake-shaped water flow channel, the removal efficiency of 5-fluorouracil reaches over 80% within 6h, and the treatment effect is obvious; the flow rate of inlet/outlet water is reasonably adjusted, the inactivation of the catalyst can be slowed down, and the maintenance cost of the device is reduced; the invention can be used for the research of catalyst inactivation mechanism and the long-term stable purification technology of medical wastewater treatment, secondary effluent of sewage treatment plants and urban drinking water.
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 (10)
1. A method for regulating and controlling catalyst activity by using a continuous flow photocatalytic reaction device is characterized by comprising the following specific steps:
s1, uniformly coating a catalyst suspension on a catalyst carrier, drying and fixing, calcining the carrier attached with the photocatalyst at 150-400 ℃ to prepare the photocatalyst, and combining the photocatalyst with a fixing frame to prepare a photocatalyst component;
s2, placing a diluent of a target pollutant in a liquid storage tank of the continuous flow photocatalytic reaction device, tightly connecting the liquid storage tank with the photocatalytic reactor through a silicone tube, respectively controlling the water inlet flow rate of the photocatalytic reactor to be 3-30 mL/min and the water outlet flow rate of the photocatalytic reactor to be 1-20 mL/min through a single-channel peristaltic pump, ensuring that the average water flow rate is 3-20 mL/min, operating the device in a continuous flow state, and changing the contact time between water flow and a fixed photocatalyst by controlling the flow rate of the water flow at the water inlet and the water outlet of the device, thereby realizing the regulation and control of the activity of the catalyst.
2. The method for regulating and controlling the activity of a catalyst by using a continuous flow photocatalytic reaction device as set forth in claim 1, wherein the catalyst suspension in step S1 is TiO2Solutions, ZnO solutions or Pd @ TiO2More than one of the solutions, the concentration of the catalyst suspension is 0.02-2 g/mL, the catalyst carrier is more than one of foamed nickel, foamed aluminum and a glass fiber membrane, and the calcining time is 4-8 h.
3. The method for regulating and controlling the activity of a catalyst by using a continuous flow photocatalytic reaction device according to claim 1, wherein the concentration of the diluent of the target pollutant in step S2 is 5-40 mg/L, the target pollutant is 5-fluorouracil, the treatment time is 3-8 hours, and the irradiation wavelength of the ultraviolet lamp is 320-410 nm.
4. The continuous-flow photocatalytic reaction device for realizing regulation and control of the activity of the catalyst according to the method of any one of claims 1 to 3, is characterized in that the photocatalytic reaction device comprises a photocatalytic reactor, a liquid storage tank and a single-channel peristaltic pump; the liquid storage tank is connected with the photocatalytic reactor through a silicone tube, and the single-channel peristaltic pump is arranged on the silicone tube and is used for controlling the flow of the fluid to be treated at the water inlet and the water outlet of the reactor; a photocatalyst component and an ultraviolet lamp set are arranged in the photocatalytic reactor; the photocatalyst component and the ultraviolet lamp group are fixed on different side surfaces of the photocatalytic reactor in a crossed manner and keep an interval with the other side surface; the photocatalyst components are arranged on two sides of the ultraviolet lamp groups in parallel at intervals, and the photocatalyst components and the adjacent ultraviolet lamp groups form a snake-shaped water flow channel.
5. The continuous flow photocatalytic reaction device as set forth in claim 4, wherein the photocatalytic assembly comprises a fixed frame and a photocatalytic net, the fixed frame being a frame with a hollow center at a middle position of the fixed frame.
6. The continuous-flow photocatalytic reaction device as set forth in claim 4, wherein the casing of the photocatalytic reactor is made of corrosion-resistant hard material; the photocatalysis net is a dense porous metal net material.
7. The continuous flow photocatalytic reaction apparatus according to claim 4, wherein the liquid storage tank includes a first liquid storage tank and a second liquid storage tank, the first liquid storage tank is provided with an output port, the second liquid storage tank is provided with an input port, and the output port and the input port are respectively connected to the photocatalytic reactor through silicone tubes.
8. The continuous-flow photocatalytic reaction device according to claim 4, wherein the ultraviolet lamp set comprises a plurality of ultraviolet lamps, the ultraviolet lamps are connected in parallel, a protective cover is arranged outside the ultraviolet lamp set, a plurality of baffles are arranged inside the protective cover at equal intervals, and the ultraviolet lamps are arranged between the baffles and used for supporting and isolating the ultraviolet lamps.
9. The continuous-flow photocatalytic reaction apparatus as set forth in claim 4 wherein the photocatalytic reactor is further provided with a water inlet and a water outlet; the single-channel peristaltic pump comprises a first single-channel peristaltic pump and a second single-channel peristaltic pump, wherein the first single-channel peristaltic pump controls the flow of the water inlet to be larger than the flow of the second single-channel peristaltic pump to control the water outlet.
10. Use of the continuous flow photocatalytic reaction device according to any one of claims 4 to 9 in the field of medical wastewater treatment, secondary effluent of sewage treatment or advanced purification of municipal drinking water.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201381244Y (en) * | 2009-04-01 | 2010-01-13 | 北京铸盟科技有限公司 | Continuous type photocatalysis oxidation treatment waste water device |
| JP2010022936A (en) * | 2008-07-18 | 2010-02-04 | Ube Ind Ltd | Apparatus and method for producing ultrapure water |
| CN101843915A (en) * | 2010-05-14 | 2010-09-29 | 蔡宇峰 | Ultraviolet catalytic oxidation deodorizing device |
| CN102463109A (en) * | 2010-11-18 | 2012-05-23 | 晓健科技（大连）有限公司 | Novel activated carbon fiber with nano-scale photocatalyst |
| US20130156654A1 (en) * | 2011-11-25 | 2013-06-20 | Jong Seop Shim | Ultraviolet sterilizer for water pipe and water way type |
| CN104066510A (en) * | 2011-11-29 | 2014-09-24 | 创新市场私人有限公司 | A photocatalyst |
| CN105169941A (en) * | 2015-09-21 | 2015-12-23 | 天津工业大学 | Indoor light cracking adsorbing gas purification device |
| CN207330427U (en) * | 2017-09-04 | 2018-05-08 | 永港伟方（北京）科技股份有限公司 | A kind of formaldehyde-containing wastewater efficient oxidation processing unit |
-
2022
- 2022-01-25 CN CN202210085323.XA patent/CN114588855B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010022936A (en) * | 2008-07-18 | 2010-02-04 | Ube Ind Ltd | Apparatus and method for producing ultrapure water |
| CN201381244Y (en) * | 2009-04-01 | 2010-01-13 | 北京铸盟科技有限公司 | Continuous type photocatalysis oxidation treatment waste water device |
| CN101843915A (en) * | 2010-05-14 | 2010-09-29 | 蔡宇峰 | Ultraviolet catalytic oxidation deodorizing device |
| CN102463109A (en) * | 2010-11-18 | 2012-05-23 | 晓健科技（大连）有限公司 | Novel activated carbon fiber with nano-scale photocatalyst |
| US20130156654A1 (en) * | 2011-11-25 | 2013-06-20 | Jong Seop Shim | Ultraviolet sterilizer for water pipe and water way type |
| CN104066510A (en) * | 2011-11-29 | 2014-09-24 | 创新市场私人有限公司 | A photocatalyst |
| CN105169941A (en) * | 2015-09-21 | 2015-12-23 | 天津工业大学 | Indoor light cracking adsorbing gas purification device |
| CN207330427U (en) * | 2017-09-04 | 2018-05-08 | 永港伟方（北京）科技股份有限公司 | A kind of formaldehyde-containing wastewater efficient oxidation processing unit |
Non-Patent Citations (3)
| Title |
|---|
| 李洪辉;郝晓刚;张忠林;刘世斌;张富国;: "迷宫流鼓泡光催化反应器结构对甲基橙降解性能的影响", 太原理工大学学报, no. 03, pages 13 - 16 * |
| 邓谦;蒋耀辉;彭振山;申晓明;韦宗元;蔡铁军;: "掺杂修饰TiO_2复合催化剂光催化消除甲醇的研究", 湖南科技大学学报(自然科学版), no. 01, pages 106 - 111 * |
| 郝晓刚;罗善霞;张忠林;樊彩梅;刘世斌;孙彦平;: "迷宫式错流鼓泡光催化反应器苯酚降解特性研究", 高校化学工程学报, no. 06, pages 150 - 153 * |
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