CN115180684A - Method and device for preparing hydrogen by applying composite photocatalyst to organic wastewater purification coupling - Google Patents
Method and device for preparing hydrogen by applying composite photocatalyst to organic wastewater purification coupling Download PDFInfo
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The invention discloses a method and a device for preparing hydrogen by applying a composite photocatalyst to organic wastewater purification coupling, and belongs to the field of wastewater treatment. The invention designs a CuO/TiO carrier 2 Wastewater treatment device of composite catalyst wire mesh, cuO/TiO 2 The composite catalyst has high catalytic efficiency, and the photocatalytic reaction degrades organic matters in the organic wastewater into small molecular substances and decomposes the water molecules into H 2 And O 2 (ii) a The device promotes the mass transfer of reactants and products in the holes of the screen by stirring; the catalyst and the wastewater can be easily separated, the wastewater does not need secondary treatment, and the catalyst can be recycled. The invention reduces the requirement of wastewater pretreatment and separates solid and liquid of the subsequent wastewaterThe separation and the deep purification are integrated, the organic matter degradation efficiency is improved, the treatment energy consumption and the treatment cost are reduced, and the aim of three purposes of wastewater treatment is fulfilled.
Description
Technical Field
The invention belongs to the field of organic wastewater treatment, and particularly relates to a method and a device for preparing hydrogen by applying a composite photocatalyst to organic wastewater purification and coupling.
Background
The proportion of industrial water in the world to the total human yield is up to 22%, and the proportion of industrial water in some industrially developed countries is up to 60%, so that the amount of industrial wastewater is huge and still increases at present. In order to avoid environmental pollution such as river soil caused by the wastewater, the wastewater needs to be subjected to harmless, recycling and reduction treatment, which is collectively called as 'three-treatment' treatment of the wastewater. The technology of three-way treatment of wastewater is crucial to protecting ecological environment. At present, industrial organic wastewater can reach the standard and be discharged only through three-stage treatment, wastewater-containing pretreatment, first-stage treatment and advanced treatment, the process is complex, and the harmless speed is low. The main technical methods adopted in the prior wastewater treatment include a filtration method, a precipitation method, a microbial degradation method, an activated carbon adsorption method and the like. However, the organic matter/heavy metal content of the industrial wastewater is high, the pH is non-neutral, and the temperature/turbidity/salinity is different, so that the existing process method has the problems of slow treatment process, large efficiency fluctuation, high cost and the like.
TiO 2 Is the most commonly used semiconductor photocatalyst at present. Irradiation of TiO by light 2 The particles excite the band gap light to generate electron-hole pairs. The photoproduction electrons can directly participate in the reduction reaction of water to generate H 2 And O 2 (ii) a Can be reacted with O 2 Superoxide hydroxyl radical or superoxide ion radical with strong oxidizing property is generated by reaction; can be reacted with H 2 O/OH - Generating hydroxyl radicals which also have strong oxidizing property; can directly participate in the oxidation reaction of organic matters, and finally mineralizes the organic matters into H 2 O and CO 2 And the like. Based on the above mechanism, nano TiO 2 Photocatalytic technology is considered to be the most effective and promising organic wastewater treatment technology.
At present, various schemes for treating organic wastewater by photocatalysis exist, and TiO is mixed into the organic wastewater most easily to implement 2 Nanopowder, but TiO 2 The nano powder is difficult to react with wastewaterSeparation, which will flow into the downstream process with the wastewater; after bubbles generated on the surface of the catalyst coat the surface of catalyst particles, ultraviolet light is refracted by the bubbles to reduce electron-hole pairs, and reactants cannot diffuse to the surface of the catalyst, so that the photocatalytic reaction efficiency is obviously reduced; when the turbidity of the wastewater is high, the photolysis efficiency of the organic matters is low due to low illumination intensity. In addition, this solution does not fulfill the resource and reduction requirements of the wastewater.
In order to recover the catalyst, CN108840390a proposes a technical method: modified TiO 2 The mixed fabric is woven on PTFE to form a filter screen, organic matters in the waste water are retained on the filter screen, and then the filter screen is taken out and exposed to the sun to decompose the organic matters. The technology has high organic matter degradation efficiency, solves the problem that the catalyst flows into downstream process equipment along with the wastewater, but has limited organic matter treatment capacity, requires frequent taking out of the filter screen for insolation in the process, and needs to collect and lay the filter screen in a transparent container before insolation, so that the organic wastewater cannot be continuously treated. If the wastewater contains impurities which can not be decomposed, the impurities are intercepted and accumulated by the filter screen and are difficult to separate, so that the organic interception amount is reduced, and finally, the organic matter degradation can not be realized.
CN109110868A provides a process for treating organic wastewater by adopting photoelectrocatalysis, the process can carry out multi-cycle degradation on the wastewater, and the process adopts a wire mesh type TiO 2 The photocatalytic material not only serves as a catalyst for photolyzing organic matters, but also serves as an anode of an electrochemical system. The technology solves the problem of compounding photoproduction electrons and holes by applying bias voltage to the whole wastewater treatment system, and simultaneously, UV light sources are arranged among all layers of silk screens to enhance photocatalytic reaction, thereby obviously improving TiO 2 Catalytic efficiency of the catalyst. However, the application of an electric field to the wastewater by the technical route increases energy consumption, especially when the wastewater treatment capacity is large and the wastewater contains high-concentration salt ions; pumps are added at the front end and the rear end of the reaction box to guide the flow of wastewater, so that particles are easily embedded into the aperture of the silk screen and are difficult to take out, and even the catalyst and the silk screen structure are damaged; for large particles in wastewater, although the screen can be used for intercepting, the intercepted large particles cannot be discharged out of the system, and the large particles need to be removed after wastewater treatment is stopped.
In summary, the main disadvantages of the prior art include:
1.TiO 2 the nano catalyst can not be recycled and reused;
2. based on TiO 2 The organic wastewater degradation technology of the nano catalyst is difficult to continuously operate;
3.TiO 2 the nano catalyst has low degradation efficiency, needs to be matched with an applied electric field, and has high energy consumption and high waste liquid treatment cost.
Disclosure of Invention
The method aims to solve the problems of low efficiency, high energy consumption and incapability of recycling the catalyst in the existing photocatalytic wastewater degradation technology. The invention provides a method and a device for preparing hydrogen by applying a composite photocatalyst to purification and coupling of organic wastewater, which reduce the requirement on wastewater pretreatment, integrate subsequent solid-liquid separation and deep purification of the wastewater, improve the degradation efficiency of organic matters, reduce the energy consumption and cost for treatment and realize the goal of wastewater treatment.
The technical scheme of the invention is as follows:
the invention firstly provides a device for preparing hydrogen by applying a composite photocatalyst to organic wastewater purification coupling, which comprises a waste liquid reaction tank and stirring equipment positioned in the waste liquid reaction tank,
the waste liquid reaction tank is internally provided with hollow cylindrical CuO/TiO 2 Composite catalyst wire mesh, said CuO/TiO 2 The composite catalyst wire mesh divides the inner area of the waste liquid reaction tank into a part which can only pass through CuO/TiO 2 A stirring area for mass transfer of the composite catalyst wire mesh and a purified wastewater area, the CuO/TiO 2 A plurality of UV lamps are arranged in the composite catalyst silk screen;
the stirring device is arranged in the stirring area, the bottom of the stirring area is in a cone shape with a sharp upper end and a thick lower end, and a plurality of sewage outlets communicated with the stirring area are arranged between the edge of the cone bottom and the side wall of the waste liquid reaction tank; the stirring district still is equipped with waste liquid retort entry, the waste water district that has purified is equipped with oxyhydrogen gas mixture export and the export of purified waste water.
According to a preferred embodiment of the present invention, said CuO/TiO 2 The top of the composite catalyst wire mesh is connected with the top of the waste liquid reaction tank, and the bottom of the composite catalyst wire mesh is communicated with the waste liquid reaction tankThe annular sealing plate is connected with the inner wall surface of the waste liquid reaction tank; the stirring zone and the purified wastewater zone can only pass through CuO/TiO 2 The composite catalyst wire mesh is in liquid communication.
According to a preferred embodiment of the present invention, the CuO/TiO is 2 The preparation method of the composite catalyst wire mesh comprises the following steps: soaking the brass wire mesh in acetone, and ultrasonically vibrating for 5-15 minutes to remove impurities on the surface of the wire mesh; transferring the brass wire mesh soaked by acetone into a high-purity helium environment, standing for 20-60 minutes until the acetone is completely volatilized, and forming the brass wire mesh without impurities on the surface; soaking the brass wire mesh in 10-20% NaCl solution in an oxygen-free environment, and heating the solution to 60-90 ℃ to accelerate the speed of dezincification of the brass; after forming porous copper on the surface of the brass wire mesh, stopping corrosion and circularly cleaning by using deionized water; placing the cleaned brass wire mesh in a reaction chamber, conveying organic alkoxide of titanium into the reaction chamber in an air environment, and pyrolyzing at 450-850 ℃; then, slowly cooling the temperature of the reaction chamber to 120-180 ℃ at a speed of less than 5 ℃/min, and preserving the temperature for 24-48 hours to form CuO/TiO 2 And (3) compounding a catalyst wire mesh.
The invention also provides a method for producing hydrogen by purifying and coupling organic wastewater based on the device, which comprises the following steps:
pressurizing the organic wastewater by a wastewater pump, sending the organic wastewater into a stirring area of a wastewater reaction tank from an inlet of the wastewater reaction tank, and turning on a stirring device and a UV lamp; the wastewater is uniformly distributed under stirring and passes through CuO/TiO under the action of centrifugal force and pump pressure generated by stirring 2 The composite catalyst wire mesh flows to the purified wastewater area;
under the irradiation of UV lamp, cuO/TiO 2 The photocatalytic reaction is generated on the surface of the composite catalyst silk screen, so that organic matters in the organic wastewater are degraded into micromolecular substances, and water molecules are decomposed into H 2 And O 2 ；
H 2 And O 2 The bubbles flowing with the wastewater into the purified wastewater zone, H 2 And O 2 The waste liquid reaction tank is separated from the oxyhydrogen mixed gas outlet; the purified wastewater is discharged from a wastewater outlet capable of recycling;
solid particles contained in organic wastewaterCuO/TiO 2 The composite catalyst wire mesh is intercepted, and solid particles flow through the bottom area of the waste liquid reaction tank under the action of gravity and turbulence disturbance, are thrown to the edge of the bottom, and can be discharged by intermittently opening a drain outlet.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention uses fine CuO/TiO 2 The composite catalyst wire mesh is a structural material, and centrifugal force is generated in the stirring area through stirring; under the action of centrifugal force and pump pressure generated by stirring, the wastewater to be treated is strengthened to pass through CuO/TiO 2 The composite catalyst wire mesh flows to the purified wastewater area; and H produced by decomposition of water molecules 2 、O 2 The bubbles can be discharged out of the silk screen by water flow in time, and the problem that the photocatalytic efficiency is reduced due to the fact that the surface bubbles refract light and influence mass transfer in the prior art is solved, so that the effect of remarkably improving the photocatalytic efficiency is achieved. Meanwhile, the invention is applicable to CuO/TiO 2 The mesh number of the composite catalyst wire mesh is selected, so that the wire mesh can play a role in intercepting solid particles in organic wastewater, turbulent disturbance of a reaction zone is aggravated by stirring, the solid particles flow through the bottom area of the waste liquid reaction tank under the action of gravity and turbulent disturbance, and are thrown to the bottom edge under the design of the pointed cone bottom, and bottom deposition is avoided.
(2) For CuO/TiO in the invention 2 The composite catalyst wire mesh is specially prepared, on one hand, through the selection of the mesh number, the waste water can be ensured to pass through the wire mesh at a certain flow rate, and the effect of intercepting solid particles can be achieved; in the second aspect, in the process of preparing the silk screen, the silk screen is corroded by NaCl solution at the temperature of 60 to 90 ℃ to form a surface porous structure, so that the surface area of the silk screen is increased, and the catalytic efficiency is improved; in a third aspect, the CuO/TiO is obtained on the surface of the silk screen with a porous structure by a heterogeneous semiconductor coupling process 2 Composite catalyst, overcomes the defects of the prior TiO 2 The problem of low catalytic efficiency of the silk screen is solved, and the existing method for adding TiO overcomes 2 The nano powder scheme has the problem of difficult separation from the wastewater.
(3) The invention adopts the organic matter degradation/water photolysis integrated technology, purifies the wastewater and produces hydrogen as a byproduct, overcomes the problem of high wastewater treatment cost in the prior art, brings economic benefits and achieves the effect of wastewater resource utilization.
(4) The invention synchronously realizes the separation of particulate matters in the wastewater and the photocatalytic reaction, and overcomes the problem that the prior art requires pretreatment to remove the particulate matters at the early stage and needs to be stopped for cleaning after the particulate matters are intercepted, thereby achieving the effect that the wastewater purification process can be operated continuously for a long time.
Drawings
Fig. 1 is a schematic structural view of a brass wire mesh in the example.
FIG. 2 is a schematic diagram of the structure of the device of the present invention.
Figure 3 is a partial cross-sectional view of a waste outlet of the apparatus of the present invention.
In the figure, 1-an organic wastewater inlet, 2-a waste liquid reaction tank inlet, 3-an oxyhydrogen mixed gas outlet, 4-a sewage discharge outlet, 5-a waste liquid reaction tank outlet, 6-a recyclable waste water outlet and 7-a waste water return pipeline; 8-waste liquid reaction tank, 9-stirring equipment, 10-CuO/TiO 2 The method comprises the following steps of (1) compounding a catalyst wire mesh, 11-a waste liquid pump, 12-a stirring area, 13-a purified waste water area and 14-a UV lamp.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments. The described embodiments are merely exemplary of the disclosure and are not intended to limit the scope thereof. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
As shown in fig. 2, this embodiment provides a device for producing hydrogen by applying a composite photocatalyst to organic wastewater purification coupling, which includes a waste liquid reaction tank 8 and a stirring apparatus 9 located in the waste liquid reaction tank 8,
the waste liquid reaction tank 8 is internally provided with a CuO/TiO reactor which is hollow cylindrical and has a certain height 2 Composite catalyst wire mesh 10, said CuO/TiO 2 The composite catalyst wire mesh 10 divides the inner area of the waste liquid reaction tank 8 into a stirring area 12 and a purified waste water area 13, and the CuO/TiO is 2 A plurality of UV lamps 14 are arranged in the composite catalyst screen 10;
the stirring device 9 is arranged in a stirring area 12, the bottom of the stirring area 12 is in a conical shape with a sharp upper end and a thick lower end, and a plurality of sewage outlets 4 communicated with the stirring area 12 are arranged between the edge of the conical bottom and the side wall of the waste liquid reaction tank 8; the stirring area 12 is also provided with a waste liquid reaction tank inlet 2, and the purified waste water area 13 is provided with an oxyhydrogen gas mixture outlet 3 and a purified waste water outlet 5.
In a preferred embodiment of the present invention, the CuO/TiO is 2 The top of the composite catalyst wire mesh 10 is connected with the top of the waste liquid reaction tank 8, the bottom of the composite catalyst wire mesh is connected with the inner wall surface of the waste liquid reaction tank 8 through an annular sealing plate, and the annular sealing plate is impermeable; so that the agitation zone 12 and the purified wastewater zone 13 can pass only CuO/TiO 2 The composite catalyst gauze 10 is in fluid communication.
In a preferred embodiment of the present invention, the CuO/TiO is 2 The central axis of the composite catalyst wire mesh 10, the central axis of the waste liquid reaction tank 8, the stirring shaft of the stirring device 9 and the central axis of the conical bottom are coaxial. The components are coaxially arranged, so that a flow field generated by stirring uniformly acts on CuO/TiO 2 On the composite catalyst screen 10, the reaction at each position on the screen is more uniform, which is helpful to improve the efficiency of the whole reaction and make the process more stable.
As shown in FIG. 2, in this embodiment, the stirring paddle of the stirring device 9 is disposed at a height of CuO/TiO 2 Between the top and bottom of the composite catalyst gauze 10. The number of layers of the stirring paddle can be single layer or multiple layers, and can be determined according to CuO/TiO 2 The height of the composite catalyst screen 10 is selected, in this example, by a double layer paddle. The shape of the paddle may be selected in accordance with the prior art and conventional knowledge of paddle selection.
In a preferred embodiment of the invention, the CuO/TiO is based on the minimum particle size requirement to be removed for wastewater purification 2 The composite catalyst wire mesh 10 takes a brass wire mesh of 500 to 3000 meshes as a carrier. CuO composite TiO is formed on the surface of the carrier 2 Photocatalyst, said CuO/TiO 2 The preparation method of the composite catalyst screen 10 comprises the following steps: soaking the brass wire mesh in acetone, and ultrasonically vibrating for 5-15 minutes to remove impurities on the surface of the wire mesh; quickly soak acetoneTransferring the brass wire mesh into a high-purity helium environment, standing for 20-60 minutes until acetone is completely volatilized, and forming the brass wire mesh without impurities on the surface; soaking the brass wire mesh in 10-20% NaCl solution in an oxygen-free environment, and heating the solution to 60-90 ℃ to accelerate the speed of brass dezincification; forming a porous structure after the dezincification of the brass wire mesh, stopping corrosion after a proper amount of surface micropores are formed, and washing the brass wire mesh with deionized water for multiple times until the resistivity of the cleaning solution exceeds 18 MOmega-M; placing the brass wire mesh in a reaction chamber, conveying organic alkoxide of titanium into the reaction chamber in an air environment, and pyrolyzing at 450-850 ℃; then, the temperature of the reaction chamber is slowly reduced to 150 ℃ at the speed of 1.5 ℃/min and is kept for 24 hours to form CuO/TiO 2 A composite catalyst gauze 10. This process is a hetero-semiconductor coupling process, also referred to as a semiconductor recombination process. CuO/TiO 2 The catalytic efficiency of the composite catalyst is far higher than that of TiO 2 Photocatalyst, due to CuO/TiO 2 The composite catalyst can not only effectively inhibit the recombination of the photo-generated electron-hole pairs, but also expand the spectral response range, thereby obviously improving the efficiency of photocatalytic decomposition without adopting electrochemical assistance.
And vertically cutting a plurality of rows of round holes on the brass wire net, uniformly distributing a plurality of round holes on each row along the circumference, and selecting the diameter of the round holes according to the size of the matched UV lamp 14. In this example, a brass wire mesh of 1000 meshes is selected and the thickness is 3cm. FIG. 1 shows the UV lamp 14 at 1000 mesh CuO/TiO 2 Radial profile of the composite catalyst gauze 10. In the presence of CuO/TiO 2 UV lamps 14 are uniformly distributed on the composite catalyst screen 10 along 2 layers of circular rings, 18 UV lamps 14 are respectively distributed on each circular ring, the diameter of each UV lamp 14 is 10mm, the UV lamps 14 are radially and crossly distributed, so that CuO/TiO is ensured 2 The ultraviolet light on the surface of the composite catalyst silk screen 10 is uniform.
As shown in figure 3, the sewage outlet 4 of the invention is schematically shown, the bottom of the waste liquid reaction tank 8 adopts a conical bottom, and the bottom can be realized by arranging an inverted V-shaped internal structure in the reaction tank, namely the center is high and the edge is low. 4 sewage outlets 4 are uniformly distributed at the bottom edge of the waste liquid reaction tank 8, and the structure of each sewage outlet 4 is shown in figure 3.
The processing principle of the invention is as follows: in the waste liquid reaction tank 8, as shown in figure 2The mounting is coated with CuO/TiO 2 A composite catalyst screen 10 (referred to simply as a screen in this paragraph). The stirring device 9 is opened to enable the waste liquid to rotate rapidly, organic pollutants are stirred to be difficult to agglomerate and distributed more uniformly in the waste water, and the centrifugal force of the organic pollutants and water is increased by the induced rotational flow effect and is driven to flow to the other side through the wire mesh; after stirring, the mass transfer of reactants and products in the mesh holes is promoted by both the wastewater flow enhancement and the boundary pressurization. Because the aperture of the silk screen is small, the flow of water continuously pushes the generated bubbles to be discharged from the silk screen, thereby reducing the influence of the bubbles on the light intensity of the surface of the catalyst to the maximum extent, improving the generation speed of photo-generated electrons and strengthening the photocatalytic reaction speed of organic matters and water on the surface of the catalyst. On the other hand, the high-speed stirring of the waste liquid can enable solid particles with larger density to move outwards due to the centrifugal effect, and the solid particles cannot penetrate through a wire mesh with the aperture smaller than the particle size, are intercepted in the stirring area 12 of the waste liquid reaction tank 8, and are quickly thrown to the bottom edge when flowing through the bottom area of the waste liquid reaction tank 8 under the action of gravity and turbulence disturbance. The bottom edge of the waste liquid reaction tank 8 is little influenced by the stirring rotational flow, and the particles are settled at the position and then can be discharged out of the waste liquid reaction tank 8 by intermittently opening the drain outlet 4. The flow rate of the waste liquid from the waste liquid reaction tank agitation zone 12 to the purified waste liquid zone 13 is realized by controlling the outlet pressure of the waste liquid pump 11 and the flow rate of the waste liquid. The pressurization of the stirring area 12 of the waste liquid reaction tank is also helpful for improving the reaction rate of photocatalytic degradation of organic matters and photocatalytic hydrogen production, and simultaneously, the particles can be impacted to prevent the blockage of the sewage outlet 4 when the particles at the bottom are discharged. CuO/TiO 2 The surface of the nano particles generates a photocatalytic reaction to degrade organic matters into small molecular substances and decompose water molecules into H 2 And O 2 See formula (1) and formula (2). Wherein part O 2 Can react on the active site to generate strong oxidizing substances such as superoxide radical and the like, and degrade organic matters. The treated wastewater does not contain organic matters, particles and other impurities and can be recycled. For organic wastewater with too high organic matter content, if complete degradation of the organic matter cannot be realized by one-time treatment, the organic wastewater can circularly enter the device for purification until the organic matter is completely decomposed. Therefore, the particulate matter is separated and the organic matter is reducedThe hydrogen production by water and hydrolysis can be simultaneously completed in the equipment.
Based on the above principle, the general process of the method of the invention is as follows: pressurizing organic wastewater by a wastewater pump 11, sending the organic wastewater into a stirring area 12 from an inlet 2 of a wastewater reaction tank, and turning on a stirring device 9 and a UV lamp 14; the wastewater is uniformly distributed under stirring and passes through CuO/TiO under the action of centrifugal force and pump pressure generated by stirring 2 The composite catalyst gauze 10 flows to the purified wastewater region 13;
under the irradiation of the UV lamp 14, cuO/TiO 2 The photocatalytic reaction is generated on the surface of the composite catalyst silk screen 10, so that organic matters in the organic wastewater are degraded into micromolecular substances, and water molecules are decomposed into H 2 And O 2 ；
CuO/TiO 2 Continuous CO generation from the catalyst surface of the composite catalyst gauze 10 2 、H 2 、O 2 In the presence of air bubbles, waste liquid in CuO/TiO 2 When the composite catalyst silk screen 10 flows, the generated micro bubbles are pushed out of the meshes in time;
H 2 and O 2 The bubbles of air flow with the wastewater into the purified wastewater zone 13 2 And O 2 The waste liquid reaction tank 8 is separated from the oxyhydrogen gas outlet 3; the purified waste water is discharged from an outlet 5 of the waste liquid reaction tank;
solid particles contained in organic wastewater are coated with CuO/TiO 2 The composite catalyst silk screen 10 intercepts, and solid particles flow through the bottom area of the waste liquid reaction tank 8 under the action of gravity and turbulence disturbance, are thrown to the edge of the bottom, and can be discharged by intermittently opening the sewage outlet 4.
In one embodiment of the present invention, an exemplary method flow is employed that: starting the waste liquid pump 11, controlling the flow of the waste liquid pump 11 to be 1L/min, and pumping the organic waste water from the organic waste water inlet 1 to the waste liquid through the waste liquid pump 11A stirring zone 12 of the reaction tank 8. The rotating speed of the stirring device 9 is adjusted to 400rpm, and when the stirring waste liquid rotates at high speed, a larger centrifugal force can be provided to realize solid-liquid separation. When the particle size of the impurities such as particles, mud blocks and the like in the waste liquid is more than 0.1 mu m, 1000-mesh CuO/TiO cannot pass through 2 The composite catalyst wire mesh 10 is arranged along the CuO/TiO under the action of centrifugal force in the stirring process 2 The juncture of the composite catalyst wire mesh 10 and the stirring area 12 of the waste liquid reaction tank flows to the bottom of the waste liquid reaction tank 8. When the wastewater is treated for about 6 hours, the filtered particles are discharged out of the waste liquid reaction tank 8 through the sewage discharge outlet 4; organic matters and water in the waste liquid can pass through CuO/TiO under the action of centrifugal force and gravity 2 The pores of the composite catalyst gauze 10 flow toward the purified wastewater region 13. Under the irradiation of the UV lamp 14, the CuO/TiO solution flows through 2 The organic matter on the surface of the composite catalyst screen 10 is degraded into small molecular inorganic matter, and the water molecules are decomposed into H 2 And O 2 . Due to CuO/TiO 2 The aperture of the composite catalyst silk screen 10 is small, and the silk screen is coated with sites with abundant photocatalytic activity, so that organic matters and water molecules can be fully photolyzed. The residual unreacted water flows out of the reaction tank from the outlet 5 of the waste liquid reaction tank. If the organic matter is completely decomposed, the organic matter flows out of the system from the recyclable waste water outlet 6 and is recycled; if the organic matters are not completely decomposed, the organic matters can be pumped into the waste liquid reaction tank 8 from the waste water return pipeline 7 again through the waste liquid pump 11 until the organic matters are completely degraded. During the reaction, H is produced 2 And O 2 And the waste liquid flows out of the hydrogen-oxygen mixed gas outlet 3 to a waste liquid reaction tank 8.UV lamp 14 with CuO/TiO 2 The composite catalyst wire mesh 10 is modular equipment, and the UV lamp 14 can be directly replaced by new one in the operation process when damaged, and CuO/TiO 2 The composite catalyst gauze 10 can also be easily taken out for maintenance.
The invention is further described below with reference to specific examples:
example 1:
1000 mesh CuO/TiO with a thickness of 3cm is used 2 The composite catalyst screen 10 was continuously energized by 36 UV lamps 14 of 5W power at a stirring speed of 400rpm, and 7-10 mesh sand grains were continuously added to the waste liquid at a speed of 10g/min at the inlet 2 of the waste liquid reaction tank, wherein the concentration of the waste liquid was 70L and 4X 10 -5 Feeding the mol/L R-6G solution circularly,the flow rate was controlled at 2L/min. And sampling and detecting the waste liquid in the storage tank every hour. The degradation rate of organic matters in 1 hour reaches 42.6 percent, the degradation rate in 2 hours reaches 68.8 percent, and the degradation rate in 6 hours reaches 82.3 percent. No sand grains are found to flow out from the waste liquid outlet. The sand grains at the sewage outlet are continuously increased and can flow out quickly. The average gas production was found to be 5.97mL/min.
Example 2:
1000 mesh CuO/TiO 4cm thick is used 2 The composite catalyst gauze 10 was continuously energized by using 54 UV lamps 14 of 5W power with a stirring speed of 400rpm, and sand grains of 7 to 10 mesh were continuously added to the injected waste liquid at a speed of 10g/min at the inlet 2 of the waste liquid reaction tank, and this example treated 70L of sand grains of 4X 10 concentration -5 And feeding the mol/L R-6G solution circularly, wherein the flow rate is controlled to be 2L/min. And sampling and detecting the waste liquid in the storage tank every hour. The degradation rate of organic matters in 1 hour reaches 58.7 percent, the degradation rate in 2 hours reaches 80.3 percent, and the degradation rate in 6 hours reaches 89.2 percent. No sand grains are found to flow out from the waste liquid outlet. The sand grains at the sewage outlet are continuously increased and can flow out quickly. The average gas production was found to be 8.45mL/min.
Example 3:
1000 mesh CuO/TiO with a thickness of 3cm is used 2 The composite catalyst gauze 10 was continuously energized by 36 UV lamps 14 of power 10W at a stirring speed of 400rpm, and 7-10 mesh sand grains were continuously added to the injected waste liquid at a speed of 10g/min at the inlet 2 of the waste liquid reaction tank, and this example treated 70L of sand grains of concentration 4X 10 -5 And feeding the mol/L R-6G solution circularly, wherein the flow rate is controlled to be 2L/min. And sampling and detecting the waste liquid in the storage tank every hour. The degradation rate of organic matters in 1 hour reaches 67.8 percent, the degradation rate in 2 hours reaches 82.2 percent, and the degradation rate in 6 hours reaches 90.6 percent. No sand flows out of the waste liquid outlet. The sand grains at the sewage outlet are continuously increased and can flow out quickly. The average gas production was measured to be 13.6mL/min.
Example 4:
1000 mesh CuO/TiO with a thickness of 3cm is used 2 The composite catalyst gauze 10 was continuously energized by 36 UV lamps 14 of 5W power at a stirring speed of 400rpm, and 7-10 mesh sand grains were continuously added to the injected waste liquid at a speed of 10g/min at the inlet 2 of the waste liquid reaction tank, and this example treated 70L of sand particles having a concentration of 1X 10 -5 Feeding the mol/L methyl orange solution circularly,the flow rate was controlled at 2L/min. And sampling and detecting the waste liquid in the storage tank every hour. The degradation rate of organic matters in 1 hour reaches 37.3 percent, the degradation rate in 2 hours reaches 62.4 percent, and the degradation rate in 6 hours reaches 77.1 percent. No sand flows out of the waste liquid outlet. The sand grains at the sewage outlet are continuously increased and can flow out quickly. The average gas production was found to be 5.52mL/min.
Comparative example 1:
1000 mesh CuO/TiO with a thickness of 3cm is used 2 The composite catalyst gauze 10 was continuously energized by 36 UV lamps 14 of 5W power, the stirring apparatus 9 was turned off, and 7-10 mesh sand grains were continuously added to the injected waste liquid at a rate of 10g/min to the inlet 2 of the waste liquid reaction tank, and 70L of the sand grains having a concentration of 4X 10 was treated in this comparative example -5 And feeding the mol/L R-6G solution circularly, wherein the flow rate is controlled to be 2L/min. And sampling and detecting the waste liquid in the storage tank every hour. The degradation rate of the organic matter in 1 hour is 12.6 percent, the degradation rate in 2 hours is 25.7 percent, and the degradation rate in 6 hours is 31.3 percent. The sand grains that the silk screen inner ring periphery blockked up along with the operation continue to increase, and inside some sand grains breakage and embedding silk screen, a large amount of bubbles of silk screen pore interior accumulation formed the race among the waste liquid flow. The oxyhydrogen gas outlet 3 has no obvious gas generation, and the gas production rate cannot be measured.
Comparative example 2:
using 1000 mesh ordinary TiO with thickness of 3cm 2 A screen mesh, continuously energized using 36 UV lamps 14 of 5W power with a stirring speed of 400rpm, continuously added 7-10 mesh sand particles to the injected waste liquid at a speed of 10g/min to the inlet 2 of the waste liquid reaction tank, and treated 70L of this comparative example at a concentration of 4X 10 -5 And feeding the mol/L R-6G solution circularly, wherein the flow rate is controlled to be 2L/min. And sampling and detecting the waste liquid in the storage tank every hour. The degradation rate of organic matters in 1 hour is 20.3 percent, the degradation rate in 2 hours is 39.2 percent, and the degradation rate in 6 hours is 54.6 percent. No sand grains are found to flow out from the waste liquid outlet. The sand grains at the sewage outlet are continuously increased and can flow out quickly. The average gas production was found to be 2.42mL/min.
According to the principle explanation and the embodiment of the invention, the catalyst and the wastewater can be easily separated, the catalyst can be recycled, the regeneration is convenient, and the wastewater does not need secondary treatment; the wastewater purification is coupled to produce hydrogen, and the byproduct hydrogen-oxygen mixed gas achieves the purposes of wastewater resource utilization and reduction; the organic matter degradation efficiency and the water photolysis efficiency are obviously improved, and the purposes of harmless and recycling of waste water are achieved; low energy consumption, less process steps and high wastewater treatment speed.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit of the invention, and these are within the scope of the invention.
Claims (10)
1. A device for preparing hydrogen by applying a composite photocatalyst to organic wastewater purification coupling comprises a waste liquid reaction tank and stirring equipment positioned in the waste liquid reaction tank, and is characterized in that,
the waste liquid reaction tank is internally provided with hollow cylindrical CuO/TiO 2 Composite catalyst wire mesh, said CuO/TiO 2 The composite catalyst wire mesh divides the inner area of the waste liquid reaction tank into a part which can only pass through CuO/TiO 2 A stirring area for mass transfer of the composite catalyst wire mesh and a purified wastewater area, the CuO/TiO 2 A plurality of UV lamps are arranged in the composite catalyst wire mesh;
the stirring device is arranged in the stirring area, the bottom of the stirring area is in a conical shape with a sharp upper end and a thick lower end, and a plurality of sewage outlets communicated with the stirring area are arranged between the edge of the conical bottom and the side wall of the waste liquid reaction tank; the stirring district still is equipped with waste liquid retort entry, the waste water district that has purified is equipped with oxyhydrogen gas mixture export and the export of purified waste water.
2. The device for purifying and coupling organic wastewater to produce hydrogen by using the composite photocatalyst as claimed in claim 1, wherein the CuO/TiO is 2 The top of the composite catalyst wire mesh is connected with the top of the waste liquid reaction tank, and the bottom of the composite catalyst wire mesh is connected with the inner wall surface of the waste liquid reaction tank through an annular sealing plate; the stirring zone and the purified wastewater zone can only pass through CuO/TiO 2 The composite catalyst wire mesh is in liquid communication.
3. According toThe device for purifying and coupling organic wastewater by using the composite photocatalyst as defined in claim 2, wherein the height of the stirring paddle of the stirring apparatus is set at CuO/TiO 2 Between the top and bottom of the composite catalyst gauze.
4. The device for purifying and coupling organic wastewater to produce hydrogen by using the composite photocatalyst as claimed in claim 1, wherein the CuO/TiO is 2 The central axis of the composite catalyst wire mesh, the central axis of the waste liquid reaction tank, the stirring shaft of the stirring device and the central axis of the conical bottom are coaxial.
5. The device for purifying and coupling organic wastewater to produce hydrogen by using the composite photocatalyst as claimed in claim 1, wherein the CuO/TiO is 2 The composite catalyst wire mesh takes a brass wire mesh with 500 to 3000 meshes as a carrier, and CuO composite TiO is formed on the surface of the carrier 2 A photocatalyst.
6. The device for purifying organic wastewater and coupling hydrogen production by using composite photocatalyst as claimed in claim 1, wherein the CuO/TiO is used as the CuO/TiO 2 The preparation method of the composite catalyst wire mesh comprises the following steps: soaking the brass wire mesh in acetone, and ultrasonically vibrating for 5-15 minutes to remove impurities on the surface of the wire mesh; transferring the brass wire mesh soaked by the acetone into a high-purity helium environment, standing for 20-60 minutes until the acetone is completely volatilized, and forming the brass wire mesh without impurities on the surface; soaking the brass wire mesh in 10-20% NaCl solution in an oxygen-free environment, and heating the solution to 60-90 ℃ to accelerate the speed of brass dezincification; after forming porous copper on the surface of the brass wire mesh, stopping corrosion and circularly cleaning by using deionized water; placing the cleaned brass wire mesh in a reaction chamber, conveying organic alkoxide of titanium into the reaction chamber in an air environment, and pyrolyzing at 450-850 ℃; then, slowly cooling the temperature of the reaction chamber to 120-180 ℃ at a speed of less than 5 ℃/min, and preserving the temperature for 24-48 hours to form CuO/TiO 2 And (4) compounding a catalyst wire mesh.
7. According to the claimsThe device for preparing hydrogen by applying the composite photocatalyst in 1 to organic wastewater purification coupling is characterized in that the UV lamp is arranged between CuO/TiO 2 The composite catalyst is uniformly distributed in the screen along the circumferential direction.
8. A hydrogen production method by organic wastewater purification coupling based on the device of any one of claims 1 to 7, which is characterized by comprising the following steps:
pressurizing the organic wastewater by a wastewater pump, sending the organic wastewater into a stirring area of a wastewater reaction tank from an inlet of the wastewater reaction tank, and turning on a stirring device and a UV lamp; the wastewater is uniformly distributed under stirring and passes through CuO/TiO under the action of centrifugal force and pump pressure generated by stirring 2 The composite catalyst wire mesh flows to the purified wastewater area;
under the irradiation of UV lamp, cuO/TiO 2 The photocatalytic reaction is generated on the surface of the composite catalyst silk screen, so that organic matters in the organic wastewater are degraded into micromolecular substances, and water molecules are decomposed into H 2 And O 2 ；
H 2 And O 2 The bubbles flowing with the wastewater into the purified wastewater zone, H 2 And O 2 The waste liquid reaction tank is separated from the oxyhydrogen mixed gas outlet; the purified wastewater is discharged from a wastewater outlet capable of recycling;
solid particles contained in organic wastewater are coated with CuO/TiO 2 The composite catalyst wire mesh is intercepted, and solid particles flow through the bottom area of the waste liquid reaction tank under the action of gravity and turbulence disturbance, are thrown to the edge of the bottom, and can be discharged by intermittently opening a drain outlet.
9. The method of claim 8, wherein the purified wastewater is discharged from the recyclable wastewater outlet, and if the required purification requirement is not met, the purified wastewater is pumped into the stirring zone again through the inlet of the waste liquid reaction tank for recycling treatment.
10. The method of claim 8, wherein the flow rate of the waste stream from the agitated zone to the clarified waste zone is controlled to a desired set point rate by controlling the waste stream pump outlet pressure and the waste stream flow rate.
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