Sewage degradation and photocatalytic hydrogen production coupling device

Abstract

The invention discloses a sewage degradation and photocatalytic hydrogen production coupling device, and belongs to the field of new energy utilization. A water storage cavity is formed in a base, a sewage conductor comprises a mounting base and a water guide table arranged on the mounting base, the mounting base is arranged on the base, a capillary conducting tissue is arranged in the mounting base, a sewage degradation assembly and a photocatalytic hydrogen production assembly are arranged on the water guide table, and the photocatalytic hydrogen production assembly is located on the downstream of the sewage degradation assembly. After sewage to be treated enters the water storage cavity, the sewage can be diffused and conveyed to the water guide table under the capillary effect of the capillary conveying tissue, then the sewage degradation assembly degrades the sewage, and the degraded pure water flows to the photocatalytic hydrogen production assembly to be subjected to photocatalytic hydrolysis hydrogen production. The photocatalytic technology is utilized to degrade the wastewater and decompose the degraded water to prepare the hydrogen energy, so that a reliable technical route can be provided for solving the problems of traditional energy exhaustion, atmospheric environment pollution and the like, and efficient utilization of the degraded pure water of a sewage degradation system is realized.

Description

Technical Field

[0001] The present invention belongs to the field of new energy utilization, relates to a photocatalytic hydrogen production technology, and particularly relates to a sewage degradation and photocatalytic hydrogen production coupling device. Background Art

[0002] Although hydrogen energy is a promising secondary clean energy source, traditional hydrogen production technologies face several challenges. For example, while water electrolysis is a mature process, it consumes significant amounts of electricity, remains costly, and relies heavily on a stable power supply. This limits its widespread adoption amidst the current energy shortage. Hydrogen production from fossil fuels, while producing significant output, also produces significant carbon emissions, which runs counter to the philosophy of low-carbon, environmentally friendly development and exacerbates the environmental burden.

[0003] Wastewater treatment is a crucial component of environmental protection. While traditional methods can remove pollutants to a certain extent, they also have numerous drawbacks. For example, the activated sludge process requires large floor space, high energy consumption, and the production of large amounts of excess sludge, resulting in high subsequent treatment costs. Chemical precipitation methods often require the addition of large amounts of chemicals, which not only increases costs but can also cause secondary pollution.

[0004] As a highly promising emerging technology, photocatalysis offers irreplaceable advantages in both organic pollutant degradation and catalytic hydrogen production, leveraging its green, pollution-free, and inexhaustible energy source. However, currently, there is no device that can simultaneously address both wastewater treatment and hydrogen energy development through photocatalysis. This results in low utilization of purified water from wastewater degradation systems, and the economic benefits remain to be improved. Summary of the Invention

[0005] The purpose of the present invention is to provide a coupled device for wastewater degradation and photocatalytic hydrogen production, which uses photocatalytic technology to degrade wastewater and simultaneously decompose the degraded water to produce hydrogen energy (HER). It not only provides a reliable technical route for solving problems such as traditional energy depletion and atmospheric environmental pollution, but also realizes the efficient utilization of pure water degraded by the wastewater degradation system, thereby solving the problems existing in the above-mentioned prior art.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] The present invention provides a sewage degradation and photocatalytic hydrogen production coupling device, comprising:

[0008] A base having a water storage cavity therein for storing sewage to be treated;

[0009] A sewage conductor, which includes an installation base and a water guiding platform arranged on the installation base. The installation base is arranged on the base, and a capillary conduction tissue is arranged in the installation base. One end of the capillary conduction tissue is communicated with the water storage cavity, and the other end is communicated with the water guiding platform to convey the sewage to be treated to the water guiding platform;

[0010] A sewage degradation component, arranged on the water guiding platform, for degrading the sewage to be treated;

[0011] A photocatalytic hydrogen production component, arranged on the water guiding platform and located downstream of the sewage degradation component. The photocatalytic hydrogen production component is used for catalytic hydrogen production of the degraded pure water generated by the sewage degradation component.

[0012] Preferably, the base is a floating body so that the sewage degradation and photocatalytic hydrogen production coupling device can float on the water surface;

[0013] The water storage cavity is opened near the bottom of the base, and an inlet and an outlet communicated with the water storage cavity are opened on the side wall of the base. When the base floats on the water surface, both the inlet and the outlet are below the water surface.

[0014] Preferably, the bottom of the installation base is hermetically inserted into the port of the water storage cavity; the water guiding platform is arranged obliquely from high to low, and the high end of the water guiding platform is connected to the top of the installation base. The sewage degradation component and the photocatalytic hydrogen production component are arranged in sequence from high to low on the water guiding surface of the water guiding platform.

[0015] Preferably, the capillary conduction tissue includes a number of capillary channels, and the bottom end of any one of the capillary channels penetrates through the bottom of the installation base, and the top end of any one of the capillary channels sequentially penetrates through the top of the installation base and the high-end area of the water guiding platform.

[0016] Preferably, the sewage degradation component is a nano-catalytic particle layer for degrading sewage, and the nano-catalytic particle layer covers the water guiding surface of the water guiding platform; the nano-catalytic particle layer has hydrophilicity, or a hydrophilic film layer is further arranged between the bottom of the nano-catalytic particle layer and the water guiding platform;

[0017] The photocatalytic hydrogen production component is a photocatalytic hydrogen production nano-catalyst layer, and the photocatalytic hydrogen production nano-catalyst layer covers the water guiding surface of the water guiding platform; the photocatalytic hydrogen production nano-catalyst layer has hydrophilicity, or the hydrophilic film layer is further arranged between the bottom of the photocatalytic hydrogen production nano-catalyst layer and the water guiding platform.

[0018] Preferably, a stepped structure for delaying the water flow velocity is arranged in the middle of the water guiding surface of the water guiding platform.

[0019] Preferably, the sewage degradation and photocatalytic hydrogen production coupling device further includes a cover plate, which is arranged upside down above the water guide table to form a sealed cavity between the cover plate and the water guide table; the sewage degradation component and the photocatalytic hydrogen production component are both arranged in the sealed cavity, and a light-transmitting window is arranged on the cover plate; an exhaust hole for discharging the produced hydrogen is also arranged on the cover plate and / or the water guide table.

[0020] Preferably, a plurality of the water guide tables are evenly distributed at intervals on the outer periphery of the top of the installation base, and the sewage degradation component and the photocatalytic hydrogen production component are sequentially arranged from high to low on the water guide surface of any one of the water guide tables, and any one of the water guide tables is configured with a cover plate.

[0021] Preferably, the installation base is a cuboid base, and one end in the height direction of the cuboid base is inserted into the port of the water storage cavity; the water guide table is a rectangular water guide table, and two rectangular water guide tables are symmetrically arranged at the other end in the height direction of the cuboid base, and the two rectangular water guide tables are respectively located on both sides in the width direction of the cuboid base; the included angle α between the axis in the length direction of any one of the rectangular water guide tables and the axis in the height direction of the cuboid base is 35° to 85°;

[0022] The cover plate is a rectangular cover plate, and the length L1 of the rectangular cover plate is equal to the length L2 of the rectangular water guide table; the length L2 of the rectangular water guide table is greater than the width L3 of the cuboid base.

[0023] Preferably, a light-transmitting opening is formed in the cover plate, and a glass plate is embedded in the light-transmitting opening to form the light-transmitting window.

[0024] The present invention has achieved the following technical effects compared with the prior art:

[0025] The sewage degradation and photocatalytic hydrogen production coupling device proposed by the present invention utilizes photocatalytic technology to degrade wastewater and simultaneously decompose the degraded water to prepare hydrogen energy (HER), which can provide a reliable technical route for solving problems such as traditional energy depletion and atmospheric environmental pollution.

[0026] In the current traditional sewage degradation system, there are few that are combined with hydrogen production reactions, that is, they cannot make good use of the purified water after degradation, and there is room for improvement in terms of economy and utilization rate. The optimization of the current traditional solar photocatalytic hydrogen production reactor is only at the catalyst level. However, from the perspective of the structure of the reactor itself, it can be observed that most of them are mainly based on reactions at the liquid phase level. The kinetic hindrance of hydrogen desorption and the loss of solar incident light energy in the liquid phase are the essential problems existing in the current hydrogen production reaction. Moreover, in conventional tests and hydrogen production systems, vacuum conditions are often required, which is closely related to reaction conditions and the properties of photocatalytic particles, etc. The hydrogen production efficiency under atmospheric pressure will be inhibited.

[0027] The present invention utilizes a capillary transport tissue as an absorption layer to introduce capillary action. At the same time, a hydrophilic thin film loaded with photocatalysts for degradation and hydrogen production is used as a reaction carrier. The device is placed in a sewage treatment pool. Under the capillary force of the capillary transport tissue, the sewage is transported to the top water guiding platform. Then, due to the coupling effect of the hydrophilic film, a liquid film is formed on the surface of the water guiding platform. Furthermore, under the action of the sewage degradation catalyst, the adsorption of large molecular particles of pollutants is carried out. The purified water generated flows to the nanometer particle layer covering photocatalytic hydrogen production on the inclined water guiding platform due to gravity, and a photocatalytic hydrogen production reaction occurs. This nanocatalytic particle layer does not contact the water layer, which is conducive to directly receiving incident light and releasing hydrogen.

[0028] In addition, thanks to the kinetic advantage conditions such as the rapid detachment of hydrogen production bubbles and weak water pressure inhibition, the present invention can be carried out under atmospheric pressure. Moreover, with the gas-liquid-solid three-phase interface of sunlight, liquid film, and nanocatalytic particles in the gas phase as the reaction layer, the utilization rate of degrading sewage while fully decomposing water to produce hydrogen is increased, the cost is reduced, and antibiotic particles can be rapidly adsorbed, etc. The effective utilization of light and water resources is realized, and the consumption of solar light energy in the liquid phase is greatly reduced. The non-powered principle reduces the demand for energy, and problems such as the difficulty of hydrogen production bubble desorption and kinetic hindrance in the liquid phase are also effectively solved.

[0029] The whole set of devices of the present invention has a complete structure, close cooperation, is simple and easy to scale up. It can not only efficiently utilize wastewater to obtain hydrogen for storage, but also has advantages such as low energy input (non-powered), net-zero carbon output, high energy utilization rate, and cost-effectiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0031] Figure 1Schematic diagram of the overall structure of the sewage degradation and photocatalytic hydrogen production coupling device disclosed in the embodiments of the present invention;

[0032] Figure 2 Perspective structure diagram of the sewage degradation and photocatalytic hydrogen production coupling device disclosed in the embodiments of the present invention;

[0033] Figure 3 Exploded structure diagram of the sewage degradation and photocatalytic hydrogen production coupling device disclosed in the embodiments of the present invention;

[0034] Figure 4 Front view structure diagram of the cover plate disclosed in the embodiments of the present invention;

[0035] Figure 5 is Figure 4 top view of;

[0036] Figure 6 Front view structure diagram of the sewage conductor disclosed in the embodiments of the present invention;

[0037] Figure 7 is Figure 6 top view of;

[0038] Figure 8 Front view structure diagram of the base disclosed in the embodiments of the present invention;

[0039] Figure 9 is Figure 8 top view of;

[0040] Figure 10 Capillary effect diagram of the sewage conductor disclosed in the embodiments of the present invention;

[0041] Figure 11 Reaction mechanism diagram of the sewage degradation and photocatalytic hydrogen production coupling device disclosed in the embodiments of the present invention.

[0042] In the figure, the reference numerals are:

[0043] 100, sewage degradation and photocatalytic hydrogen production coupling device;

[0044] 1, base; 11, water storage cavity; 12, stepped port; 13, gas storage cavity; 14, bottom plate; 15, water inlet; 16, water outlet;

[0045] 2, sewage conductor; 21, installation base; 211, insertion protrusion; 22, water guiding platform; 23, capillary conduction tissue; 24, hydrophilic film layer; 25, stepped structure;

[0046] 3, sewage degradation component;

[0047] 4, photocatalytic hydrogen production component;

[0048] 5. Cover plate; 51. Exhaust hole; 52. Translucent window; 53. Translucent opening; 54. Glass plate

[0049] 6. Sealing ring Specific implementation manner

[0050] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0051] The object of the present invention is to provide a sewage degradation and photocatalytic hydrogen production coupling device, which uses photocatalytic technology to degrade wastewater and simultaneously decompose the degraded water to prepare hydrogen energy (HER). It can not only provide a reliable technical route for solving problems such as traditional energy depletion and atmospheric environmental pollution, but also realize the efficient utilization of pure water in the sewage degradation system to solve the problems existing in the prior art.

[0052] To make the above objects, features, and advantages of the present invention more obvious and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific implementation manners.

[0053] Embodiment 1

[0054] As Figures 1 to 3As shown, this embodiment proposes a sewage degradation and photocatalytic hydrogen production coupling device 100, including a base 1, a sewage conductor 2, a sewage degradation component 3 and a photocatalytic hydrogen production component 4. The base 1 is provided with a water storage chamber 11, which is used to hold the sewage to be treated; the sewage conductor 2 includes a mounting base 21 and a water guide platform 22 arranged on the mounting base 21, the mounting base 21 is arranged on the base 1, and a capillary conduction tissue 23 is provided in the mounting base 21, and one end of the capillary conduction tissue 23 is connected to the water storage chamber 11, and the other end of the capillary conduction tissue 23 is connected to the water guide platform 22 to transport the sewage to be treated in the water storage chamber 11 to the water guide platform 22; the sewage degradation component 3 is arranged on the water guide platform 22, and is used to degrade the sewage to be treated; the photocatalytic hydrogen production component 4 is arranged on the water guide platform 22 and is located downstream of the sewage degradation component 3. The photocatalytic hydrogen production component 4 is used to receive the degraded pure water generated by the sewage degradation component 3, and catalytically produce hydrogen using the degraded pure water as a raw material. During use, ensure that the photocatalytic hydrogen production assembly 4 is exposed to sunlight. Under the action of external components such as a water pump, the wastewater to be treated can enter the water storage chamber 11 within the base 1, then contact the capillary conduction structure 23 within the mounting base 21. Under the capillary effect of the capillary conduction structure 23, the wastewater can diffuse and be transported to the water guide platform 22. Under the directional guidance of the water guide platform 22, the wastewater first reaches the wastewater degradation assembly 3. After the wastewater degradation assembly 3 degrades the wastewater, the degraded pure water continues to flow to the photocatalytic hydrogen production assembly 4 under the directional guidance of the water guide platform 22. After absorbing sunlight, the photocatalytic hydrogen production assembly 4 can photocatalytically hydrolyze the pure water to produce hydrogen. The generated hydrogen can be collected and stored using appropriate equipment.

[0055] In some embodiments, in order to further reduce the energy consumption of the sewage degradation and photocatalytic hydrogen production coupling device 100, the base 1 can be configured with a floating function, so that the coupling device as a whole can float on the water surface, and the sewage can automatically enter the water storage chamber 11, eliminating the use of components such as water pumps, thereby reducing the energy consumption of the system; in conjunction with the capillary conduction tissue 23 set in the installation base 21, the system basically realizes unpowered water intake and unpowered water transportation, does not rely on electrical equipment, can be used for a long time, and is not limited to any application place.

[0056] In some feasible embodiments, the ways to endow the base 1 with a floating function include, but are not limited to, configuring a float for the base 1 or setting the base 1 itself as a floating body. Taking the case of setting the base 1 itself as a floating body, the base 1 serves both as a carrier for the sewage conductor 2, the sewage degradation component 3, and the photocatalytic hydrogen production component 4, and as a buoyancy support for the sewage conductor 2, the sewage degradation component 3, and the photocatalytic hydrogen production component 4, so that the entire sewage degradation and photocatalytic hydrogen production coupling device 100 can float on the water surface. Based on this, the water storage cavity 11 is preferably opened near the bottom of the base 1 and located at the center of the base 1. The side wall of the base 1 is provided with a water inlet 15 and a water outlet 16 communicating with the water storage cavity 11. When the base 1 floats on the water surface, both the water inlet 15 and the water outlet 16 are below the water surface, facilitating the real-time entry of water into the water storage cavity 11 through the water inlet 15, ensuring that the water in the water storage cavity 11 is in a dynamically flowing state, and enabling the real-time dynamic update of the sewage water body to be treated in the water storage cavity 11. It should be noted that the unfolded area of the base 1 is large enough to ensure that there is sufficient buoyancy to stably float the entire sewage degradation and photocatalytic hydrogen production coupling device 100 on the water surface; at the same time, the water storage cavity 11 is preferably a slit cavity, which can not only provide enough sewage volume to the capillary conduction tissue 23, but also ensure that when the water storage cavity 11 is full of water, it does not affect the buoyancy of the base 1.

[0057] In some embodiments, after the base 1 is set as a floating body, in order to further improve the floating performance of the base 1, an air storage cavity 13 with an opening facing down can be opened at the bottom of the base 1. The air storage cavity 13 is spaced from the aforementioned water storage cavity 11; air is stored in the air storage cavity 13, and the bottom surface of the base 1 is provided with a bottom plate 14 for sealing the air storage cavity 13 to ensure the tightness of the air storage cavity 13. When the base 1 floats on the water surface, it contacts the water through the bottom plate 14.

[0058] In some embodiments, the base 1 is in the shape of a circular disc, a rectangular disc or other polygonal discs. The water storage cavity 11 is formed at the center of the base 1, and the top of the water storage cavity 11 is open. A sunken groove structure is provided at the opening to form a stepped port 12. The mounting base 21 is preferably columnar, such as a quadrangular prism or a cylinder, and its axis is perpendicular to the base 1. A plugging protrusion 211 adapted to be plugged into the stepped port 12 is provided at the bottom of the mounting base 21. The bottom of the mounting base 21 is hermetically plugged into the stepped port 12 of the water storage cavity 11 through the plugging protrusion 211. The mounting base 21 and the water storage cavity 11 are plugged by means of a concave-convex structure, which facilitates the formation of a stable contact between the mounting base 21 and the base 1. To ensure a firm connection, after the mounting base 21 is plugged into the water storage cavity 11, it can be further fixed by bonding or welding. It should be noted that the area of the base 1 located outside the peripheral of the top opening of the water storage cavity 11 is wide enough to prevent the overall tilting of the device due to the too long structure of the water guiding platform 22 or the excessive weight of the sewage conductor 2, the sewage degradation component 3 and the photocatalytic hydrogen production component 4. That is, the base 1, as a floating body, can effectively prevent the hidden danger of unstable system operation. The whole base 1 can be made of lightweight materials with a density smaller than that of water, including but not limited to aluminum foam, porous foamed plastics, etc., to ensure the self-floating characteristic of the device.

[0059] In some embodiments, the mounting base 21 has a sufficient height to ensure that when the base 1 floats on the water surface, the photocatalytic hydrogen production component 4 is always at a certain distance above the water surface, avoiding the direct contact between the catalyst and the pollutants in the sewage and improving the recyclability of the catalyst.

[0060] To further enhance the water guiding performance of the water guiding platform 22, it is preferably arranged obliquely from high to low, and the high end of the water guiding platform 22 is connected to the top of the mounting base 21. The sewage degradation component 3 and the photocatalytic hydrogen production component 4 are arranged in sequence from high to low on the water guiding surface of the water guiding platform 22, so that the water can flow smoothly through the sewage degradation component 3 and the photocatalytic hydrogen production component 4 under the action of gravity.

[0061] In some embodiments, the specific structural form of the capillary transport tissue 23 includes, but is not limited to, capillary pores. When the capillary transport tissue 23 is provided as multiple capillary pores, the bottom end of any one capillary pore penetrates through the bottom of the mounting base 21, and the top end of any one capillary pore sequentially penetrates through the top of the mounting base 21 and the high-end area of the water guide table 22. Based on this, a microporous array is formed on the surface of the bottom of the mounting base 21 and the high-end area of the water guide table 22. The mounting base 21 is preferably made of a hydrophilic material, such as a porous material or an artificially prepared orifice plate; the capillary pores can be formed by inserting a metal tube with a hydrophilic coating on the inner wall along the height direction of the mounting base 21 into the mounting base 21. The inner cavity of any metal tube serves as a capillary pore. The hydrophilicity of the hydrophilic coating in the capillary pore is higher than that of the mounting base 21, and the setting of the hydrophilic coating in the capillary pore is beneficial to the better and faster spreading and transportation of sewage. The metal tube includes, but is not limited to, a steel tube; the hydrophilic coating in the metal tube can be made by electrospinning technology, and a porous fiber is selected as the base material, such as: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), etc. According to different hydrophilic modification methods (configuring different modifiers), the contact angle between its surface and water can be changed, so as to improve the hydrophilicity of the surface of the hydrophilic film layer.

[0062] Further, it is preferred that the pore diameter D of the capillary pore is 0.01 mm to 1 mm; the pore spacing between any adjacent pores is 2D to 10D.

[0063] In some embodiments, the sewage degradation component 3 is a nano-catalytic particle layer for degrading sewage, and the nano-catalytic particle layer covers the water guide surface of the water guide table 22. For different sewage systems, different catalyst / adsorbent particles can be selected for the nano-catalytic particle layer to form a specific degradation layer. For example, for antibiotic wastewater, catalytic particles such as Bi / g-C3N4 (bismuth-doped carbon nitride), ZnxCd1-xS (nano-particles composed of zinc (Zn), cadmium (Cd) and sulfur (S) elements) can be used. For wastewater containing trinitrotoluene (TNT), composite catalyst particles such as Co3O4 / BiVO4 (cobalt tetroxide / bismuth vanadate) can be used. For wastewater containing colored dyes, particles such as graphene oxide and graphitic carbon nitride can be used. Due to different compositions, the nano-catalytic particle layer has the ability to degrade wastewater containing various impurities, enabling the device to be systematically and multi-scenically applied in sewage degradation. Among them, it is preferred that the nano-catalytic particle layer is loaded on a hydrophilic film layer 24, that is, the bottom of the nano-catalytic particle layer is connected to the water guide table 22 through the hydrophilic film layer 24. The nano-catalytic particle layer can be loaded on the hydrophilic film layer 24 by spraying method, suction filtration method and other methods.

[0064] In some embodiments, the photocatalytic hydrogen production component 4 is a photocatalytic hydrogen production nanocatalyst layer, which covers the water-conducting surface of the water-conducting platform 22. The hydrogen production catalyst used can be a simple catalytic material such as titanium dioxide, cadmium sulfide, strontium titanate, etc., or an efficient composite hydrogen production catalytic material can be obtained through a certain preparation process, such as composite catalyst particles containing metal cocatalysts. Preferably, the photocatalytic hydrogen production nanocatalyst layer is loaded on a hydrophilic membrane layer 24, that is, the bottom of the photocatalytic hydrogen production nanocatalyst layer is connected to the water-conducting platform 22 through a hydrophilic membrane layer 24.

[0065] The hydrophilic membrane layer 24 below the photocatalytic hydrogen production component 4 and the hydrophilic membrane layer 24 below the nanocatalytic particle layer can be connected as a whole and cover the entire water-conducting surface of the water-conducting platform 22; the microporous array of the capillary transport tissue 23 on the surface of the water-conducting platform 22 is combined with the hydrophilic membrane layer 24 on the surface of the water-conducting platform 22, so that after the sewage reaches the surface of the water-conducting platform 22 through the capillary transport tissue 23, it can spread as quickly as possible and form a stable liquid film layer. Due to the design of the water-conducting platform 22 with a certain inclination angle, the formed liquid film flows smoothly towards the lower end under the action of gravity. The rising speed of the liquid is mainly affected by the hydrophilicity of the inner wall material of the capillary pores. The hydrophilic membrane layer 24 and the inclined design on the surface of the water-conducting platform 22 enable the sewage sucked up due to capillary action to mainly utilize the inclined effect and spread quickly on the surface of the water-conducting platform 22 to form a liquid film layer. Under the action of gravity, if the inclination angle of the water-conducting platform 22 is small, the flow rate will be slow, and the efficiency of degrading sewage and producing hydrogen will be low, but the performance is good; if the inclination angle of the water-conducting platform 22 is large, the flow rate will be fast and the treatment efficiency will be fast, but the performance will be poor. Therefore, for the inclination angle design of the water-conducting platform 22, there is a balance point between the treatment efficiency and the hydrogen production performance. Preferably, the angle α between the axis in the length direction of the water-conducting platform 22 and the axis in the height direction of the cuboid base is 35° to 85°.

[0066] In some embodiments, the thickness of the hydrophilic membrane layer 24 is preferably 0.01 mm to 5 mm, the average pore diameter is 0.01 μm to 10 μm, and the base material is porous fiber, which is prepared by the electrospinning process. The contact angle between its surface and water can be changed according to different hydrophilic modification methods (configuring different modifiers).

[0067] In some embodiments, a stepped structure 25 for delaying the water flow rate is provided in the middle of the water-conducting surface of the water-conducting platform 22. The stepped structure 25 is preferably arranged in the area where the sewage degradation component 3 is located. The stepped structure 25 has multiple steps opposite to the water flow direction, which can slow down the downward movement speed of the liquid, extend the sewage degradation time, and thus improve the sewage treatment effect. It should be noted that when the hydrophilic membrane layer 24 covers the stepped structure 25, it is laid on the surface of the stepped structure 25 in an attached manner.

[0068] In some embodiments, the sewage degradation and photocatalytic hydrogen production coupling device 100 further includes a cover plate 5, which is reversely arranged above the water guiding platform 22 to form a sealed cavity between the cover plate 5 and the water guiding platform 22; the sewage degradation component 3 and the photocatalytic hydrogen production component 4 are both arranged in the sealed cavity, and a light-transmitting window 52 is arranged on the cover plate 5 to ensure that sunlight can irradiate the sewage degradation component 3 and the photocatalytic hydrogen production component 4; an exhaust hole 51 for discharging the produced hydrogen is also arranged on the cover plate 5 and / or the water guiding platform 22. As a preferred solution, the exhaust hole 51 can be opened only on the cover plate 5, and the opening position of the exhaust hole 51 is not limited. It can be located on the side wall of the cover plate 5 or on the top plate surface of the cover plate 5, as long as it is close to the photocatalytic hydrogen production component 4. During actual use, the exhaust hole 51 can be connected through a gas transmission pipeline, and the hydrogen can be transported and stored in a gas storage tank by means of the water displacement method, vacuum pumping or carrier gas carrying. When the exhaust hole 51 is not connected to the gas transmission pipeline, a sealing plug can be configured to ensure the sealing performance of the sealed cavity and prevent hydrogen leakage and waste.

[0069] In some embodiments, both the cover plate 5 and the water guiding platform 22 are preferably box structures with a certain depth, and the outer peripheral dimension of the cover plate 5 is adapted to the inner cavity dimension of the water guiding platform 22. During installation, the cover plate 5 is buckled in the water guiding platform 22, and the two are in clearance fit. In order to ensure the connection sealing performance between the cover plate 5 and the water guiding platform 22, a sealing ring 6 is also arranged between the outer side wall of the cover plate 5 and the inner wall side of the water guiding platform 22.

[0070] In some embodiments, a light-transmitting opening 53 is opened in the area of the cover plate 5 above the sewage degradation component 3 and the photocatalytic hydrogen production component 4, and a glass plate 54 is embedded in the light-transmitting opening 53 to form the aforementioned light-transmitting window 52. The glass plate 54 is preferably modified light-transmitting glass, which can make solar energy better concentrate on the degradation catalyst and hydrogen production catalyst. And the modified surface of the glass is hydrophilic, which is beneficial to the spreading of surface water vapor and avoids affecting the light transmittance, thus being beneficial to the improvement of hydrogen production efficiency. The glass plate 54 is preferably made of high-transmittance quartz glass, and the glass thickness is 0.1 mm to 5 mm. It can be installed in the light-transmitting opening 53 by gluing. The position requirement of the glass plate 54 is that it is directly below the area where the sewage degradation component 3 and the photocatalytic hydrogen production component 4 are located, and can expose the sewage degradation component 3 and the photocatalytic hydrogen production component 4 entirely within the field of view of the glass plate 54, so that the sewage degradation component 3 and the photocatalytic hydrogen production component 4 can efficiently absorb sunlight through the glass plate 54.

[0071] In some embodiments, a plurality of water guiding platforms 22 are evenly distributed at intervals on the outer periphery of the top of the installation base 21, such as two, three, four, etc. The sewage degradation component 3 and the photocatalytic hydrogen production component 4 are sequentially arranged from high to low on the water guiding surface of any one water guiding platform 22, and a cover plate 5 is configured on any one water guiding platform 22.

[0072] In some embodiments, the mounting base 21 is preferably a rectangular parallelepiped base, and one end of the rectangular parallelepiped base in the height direction (ie Figure 1 The bottom end shown) is connected to the port of the water storage chamber 11; the water guide platform 22 is a rectangular water guide platform, and the other end of the height direction of the rectangular base (ie Figure 1 Two rectangular water guide platforms are symmetrically arranged (as shown in the top), and the two rectangular water guide platforms are located on both sides of the width direction of the rectangular base. The high ends of the two rectangular water guide platforms intersect to form an inverted "V" roof shape. The angle α between the longitudinal axis of any rectangular water guide platform and the height axis of the rectangular base is 35° to 85°. Correspondingly, the cover plate 5 is a rectangular cover plate. Based on the above structural design, when designing the sewage degradation and photocatalytic hydrogen production coupling device 100, the dimensions can refer to the following scheme:

[0073] like Figures 1 to 9 As shown, the top plate thickness of the cover plate 5 is H1, the top plate length is L1, the light-transmitting opening 53 passes through the top plate thickness direction of the cover plate 5, and a sinking structure is provided at one end of the light-transmitting opening 53 away from the water guide platform 22, thereby forming a first layer of groove and a second layer of groove in the light-transmitting opening 53, wherein the first layer of groove is used to embed the glass plate 54, and the height of the first layer of groove is H 11 , the groove width along the length direction of the cover plate 5 is L 11 , the height of the second layer of groove is H 12 , the groove width along the length direction of the cover plate 5 is L 12 , L 12 <L 11 <L1, and H 11 +H 12 =H1,H 11 =H 12 Correspondingly, the height of the water guide platform 22 is H2, the length is L2, the height of the mounting base 21 is H3, the width is L3, and the height of the plug-in protrusion 211 is H 31 , width is L 31 The total thickness of the base 1 is H4, the total width is L4, and the height (depth) of the stepped port 12 is H 41 , width is L 41 The height (depth) of the water storage chamber 11 is H 42 , width is L 42 , where L1=L2>L3, H 31 =0.2H3~0.5H3, L 31 <L 42 , and L 42 =0.9L 41 -0.99L 41 , L 31 <L 42 The design ensures that the bottom end of the mounting base 21 extends into the water storage chamber 11, making it easier for the capillary tissue to contact the sewage.

[0074] In some embodiments, the mounting base 21, the water guide table 22, the cover plate 5, and the base 1 are preferably manufactured by means of machining, laser engraving, etc. The material of at least one of the mounting base 21, the water guide table 22, and the cover plate 5 is a polymer material such as PMMA (plexiglass), PVDF (polyvinylidene fluoride), PEEK (polyetheretherketone), PCB, etc., or a metal material such as aluminum or stainless steel.

[0075] In summary, the sewage degradation and photocatalytic hydrogen production coupling device 100 proposed in this solution is essentially a solar photocatalytic non-powered wastewater degradation and hydrogen production coupling device, and its usage method is as follows:

[0076] Place the entire sewage degradation and photocatalytic hydrogen production coupling device 100 in a sewage treatment pool, and the base 1 supports the entire device. The sewage in the sewage treatment pool flows dynamically in the water storage cavity 11 and is transported to the hydrophilic film layer 24 on the surface of the water guide table 22 under the capillary action of the capillary transport tissue 23 in the sewage conductor 2. Under the combined action of the capillary effect and the hydrophilic film layer, a stable liquid film layer is formed on the surface of the water guide table 22, and then it flows to the nano-catalytic particle layers on both sides for photocatalytic degradation reaction; then the generated pure water automatically flows to the photocatalytic hydrogen production assembly 4 under the inclination of the water guide table 22. Under the action of the light-transmitting window 52, sunlight is reflected and focused on the nano-photocatalytic hydrogen production particle layer for photocatalytic water splitting reaction to generate hydrogen. The generated hydrogen can be transported under the control of a pressure gauge and a valve and stored in a gas storage tank by the water displacement method.

[0077] In actual operation, the process conditions of the sewage degradation and photocatalytic hydrogen production coupling device 100 can be as follows:

[0078] Select wastewater containing antibiotics; the hydrophilic membrane is made of PEI material, and is configured into a pre-solution membrane with PVP, NMP, and DMF. The average pore size is 1 micron and the thickness is 0.5 mm. It is washed in absolute ethanol to remove the PVP material and then modified to a super-hydrophilic membrane surface; the catalyst particles for photocatalytic degradation of antibiotic-containing wastewater are made of bismuth-doped carbon nitride (Bi / g-C3N4) material, and the nano-catalytic particles for overall water splitting hydrogen production are made of aluminum-doped strontium titanate (AI-SrTiO3) material with an average particle size of 100 nm. The thickness of the glass plate 54 is 1.5 mm, the thickness H1 of the top plate of the cover plate 5 is 3 mm, the length L1 of the top plate is 60 mm, the width W1 of the top plate is 40 mm, and the height H of its first-layer groove 11 = 1.5 mm, width L 11 = 18 mm, length W 11 = 32 mm, the height of the second-layer groove is H 12 = 1.5 mm, width is L 12 = 14 mm, length W 12= 32 mm; the height H2 of the water guide table 22 is 4 mm, the length L2 is 60 mm, the height H3 of the installation base 21 is 20 mm, the width L3 is 35 mm, and the height H of the insertion protrusion 211 31 = 3 mm, width L 31 = 30 mm. The capillary pore channels in the installation base 21 are of microporous structure. The diameter of the micropores (pore channels) is 1 mm, and the distance between any two connected micropores is 5 mm; the total thickness H4 of the base 1 is 10 mm, the total width L4 is 65 mm, and the height (depth) H of the stepped port 12 41 = 3 mm, width L 41 = 35 mm, the height (depth) H of the water storage chamber 11 42 = 3 mm, width L 42 = 30 mm, the width L of the gas storage chamber 13 43 = 61 mm, height H 43 = 3 mm. The pore diameters of the water inlet 15 and the water outlet 16 are both 2 mm.

[0079] Based on the above process conditions, the results of wastewater degradation and hydrogen production are as follows: Through gas chromatography quantitative detection, the photocatalytic degradation rate of antibiotic-containing wastewater and the hydrogen production and oxygen production activities of photocatalytic overall water splitting are 540 μmol / h and 270 μmol / h respectively.

[0080] The system of the proposed capillary-action-based bionic transport tissue for non-powered solar photocatalytic degradation of antibiotic-containing wastewater and coupled hydrolysis hydrogen production in this scheme uses photocatalytic technology to achieve wastewater degradation and simultaneously decompose the degraded water to prepare hydrogen energy (HER), which can provide a reliable technical route for solving problems such as traditional energy depletion and atmospheric environmental pollution. The specific beneficial effects are as follows:

[0081] (1) Compared with the plate-type fixed bed and the tube-type fluidized bed, this scheme uses a hydrophilic membrane as the carrier of the powder photocatalyst, making the loaded nano-catalytic particle layer near the gas-liquid two-phase interface layer. By regulating the capillary effect of the orifice plate and the surface hydrophilicity and hydrophobicity of the hydrophilic membrane, the liquid-phase water penetrates from the lower surface of the thin film to the upper surface under the drive of capillary force and forms a liquid film. The water guide table with a certain angle enables the antibiotics in the wastewater to be adsorbed on the catalyst layer for degradation. Due to the inclination of the water guide table, the obtained pure water can flow naturally to the catalyst layers for hydrogen production on both sides under the action of gravity for overall water splitting hydrogen production effect. During the infiltration process from bottom to top, the water molecules are in full contact with the loaded powder photocatalyst, and the reactions of photocatalytic degradation of sewage and coupled water hydrogen production occur.

[0082] (2) In the current traditional sewage degradation system, there are few that can be combined with hydrogen production reactions, that is, they cannot make good use of the purified water after degradation, and there is room for improvement in terms of economy and utilization rate. The optimization of the current traditional solar photocatalytic hydrogen production reactor is only at the catalyst level. However, from the perspective of the structure of the reactor itself, most of them are mainly based on liquid-phase reactions. The kinetic hindrance of hydrogen desorption and the loss of solar incident light energy in the liquid phase are the essential problems existing in the current hydrogen production reaction. Moreover, in conventional tests and hydrogen production systems, vacuum conditions are often required, which is closely related to reaction conditions and the properties of photocatalytic particles. The hydrogen production efficiency under atmospheric pressure will be inhibited.

[0083] This solution uses capillary conducting tissue as the absorption layer to introduce capillary action. At the same time, a hydrophilic thin film is used to load the photocatalysts for degradation and hydrogen production as the reaction carrier. The device is placed in a sewage treatment pool. Under the capillary force of the capillary conducting tissue, the sewage is transported to the top water guiding platform. Then, due to the coupling effect of the hydrophilic film, a liquid film is formed on the surface of the water guiding platform. Furthermore, under the action of the sewage degradation catalyst, the adsorption of large molecular pollution particles is carried out. The purified water generated flows to the nano-particle layer covering photocatalytic hydrogen production on the inclined water guiding platform due to gravity for photocatalytic hydrogen production reaction. This nano-catalytic particle layer does not contact the water layer, which is beneficial for directly receiving incident light and releasing hydrogen.

[0084] Benefiting from kinetic advantage conditions such as the rapid detachment of hydrogen production bubbles and weak water pressure inhibition, this solution can be carried out under atmospheric pressure. Moreover, with the gas-liquid-solid three-phase interface of sunlight, liquid film, and nano-catalytic particles in the gas phase as the reaction layer, it enables the improvement of the utilization rate of degrading sewage while fully decomposing water to produce hydrogen, cost reduction, rapid adsorption of antibiotic particles, etc., realizes the effective utilization of light and water resources, and greatly reduces the consumption of solar light energy in the liquid phase. The non-powered principle reduces the demand for energy, and problems such as the difficulty of hydrogen production bubble desorption and kinetic hindrance in the liquid phase are also effectively solved, providing an idea for improving the photocatalytic degradation of sewage and coupling hydrogen production efficiency at the essential level.

[0085] (3) The whole set of device has a complete structure, close cooperation, is simple and easy to scale up. It can not only efficiently utilize wastewater to obtain hydrogen for storage, but also has advantages such as low energy input (non-powered), net-zero carbon output, high energy utilization rate, and cost-effectiveness.

[0086] Example 2

[0087] In this embodiment, a sewage degradation and photocatalytic hydrogen production coupling device 100 is proposed. The difference from Embodiment 1 is that in this embodiment, the double-layer membrane structure design combining the nano-catalytic particle layer and the hydrophilic membrane layer 24 is replaced with a single-layer membrane that has both superhydrophilic ability and can degrade sewage simultaneously. That is, when preparing the precursor solution for making the hydrophilic membrane, the corresponding degradation catalyst is added thereto. At the same time, in this embodiment, the double-layer membrane structure design combining the photocatalytic hydrogen production nano-catalyst layer and the hydrophilic membrane layer 24 is replaced with a single-layer membrane that has both superhydrophilic ability and can produce hydrogen simultaneously. That is, when preparing the precursor solution for making the hydrophilic membrane, the corresponding hydrogen production catalyst is added thereto.

[0088] The above single-layer membrane that has both superhydrophilic ability and can degrade sewage simultaneously and the single-layer membrane that has both superhydrophilic ability and can produce hydrogen simultaneously can be set as a whole, that is, a single-layer membrane that has both superhydrophilic ability and can degrade sewage / produce hydrogen simultaneously is covered on the water guide table. That is, when preparing the precursor solution for making the hydrophilic membrane, the corresponding catalyst is added thereto, such as: PVDF / TiO2 membrane, graphene oxide / polyacrylonitrile (GO / PAN) membrane, etc.

[0089] It should be noted that the structures, ratios, sizes, etc. depicted in the drawings of this specification are only used to cooperate with the content disclosed in the specification for those skilled in this technology to understand and read, and are not used to limit the limited conditions under which the present invention can be implemented. Therefore, they do not have a substantial technical meaning. Any modification of the structure, change of the proportional relationship, or adjustment of the size, without affecting the efficacy that the present invention can produce and the purpose that can be achieved, should still fall within the scope covered by the technical content disclosed in the present invention. At the same time, the terms such as "upper", "lower", "left", "right", "middle", and "one" cited in this specification are only for the convenience of narration and clarity, and are not used to limit the scope under which the present invention can be implemented. The change or adjustment of their relative relationships, without substantial change in the technical content, should also be regarded as the scope under which the present invention can be implemented.

[0090] In the present invention, specific examples are used to elaborate the principle and implementation manner of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A sewage degradation and photocatalytic hydrogen production coupling device, characterized in that, Comprising: A base (1) with a water storage chamber (11) formed therein, where the water storage chamber (11) is used to hold the sewage to be treated; A sewage conductor (2), which includes a mounting base (21) and a water guiding platform (22) arranged on the mounting base (21). The mounting base (21) is arranged on the base (1), and a capillary conduction tissue (23) is arranged in the mounting base (21). One end of the capillary conduction tissue (23) is communicated with the water storage chamber (11), and the other end is communicated with the water guiding platform (22) to convey the sewage to be treated to the water guiding platform (22); A sewage degradation component (3) arranged on the water guiding platform (22) for degrading the sewage to be treated; A photocatalytic hydrogen production component (4) arranged on the water guiding platform (22) and located downstream of the sewage degradation component (3). The photocatalytic hydrogen production component (4) is used for catalytic hydrogen production of the degraded pure water generated by the sewage degradation component (3).

2. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 1, characterized in that The base (1) is a floating body so that the sewage degradation and photocatalytic hydrogen production coupling device can float on the water surface; The water storage chamber (11) is opened near the bottom of the base (1), and an inlet (15) and an outlet (16) communicated with the water storage chamber (11) are opened on the side wall of the base (1). When the base (1) floats on the water surface, both the inlet (15) and the outlet (16) are below the water surface.

3. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 2, wherein The bottom of the mounting base (21) is hermetically inserted into the port of the water storage chamber (11); the water guiding platform (22) is arranged obliquely from high to low, and the high end of the water guiding platform (22) is connected to the top of the mounting base (21). The sewage degradation component (3) and the photocatalytic hydrogen production component (4) are arranged in sequence from high to low on the water guiding surface of the water guiding platform (22).

4. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 3, wherein The capillary conduction tissue (23) includes a number of capillary channels. The bottom end of any one of the capillary channels penetrates through the bottom of the mounting base (21), and the top end of any one of the capillary channels penetrates through the top of the mounting base (21) and the high end area of the water guiding platform (22) in sequence.

5. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 4, wherein The sewage degradation component (3) is a nano-catalytic particle layer for degrading sewage, and the nano-catalytic particle layer covers the water guiding surface of the water guiding platform (22); the nano-catalytic particle layer has hydrophilicity, or a hydrophilic film layer (24) is further arranged between the bottom of the nano-catalytic particle layer and the water guiding platform (22); The photocatalytic hydrogen production component (4) is a photocatalytic hydrogen production nano-catalyst layer, and the photocatalytic hydrogen production nano-catalyst layer covers the water guiding surface of the water guiding platform (22); the photocatalytic hydrogen production nano-catalyst layer has hydrophilicity, or the hydrophilic film layer (24) is further arranged between the bottom of the photocatalytic hydrogen production nano-catalyst layer and the water guiding platform (22).

6. The sewage degradation and photocatalytic hydrogen production coupling device according to any one of claims 3 to 5, characterized in that In the middle of the water guiding surface of the water guiding platform (22), a stepped structure (25) for delaying the water flow velocity is arranged.

7. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 4 or 5, characterized in that Further included is a cover plate (5), which is reversely arranged above the water guide table (22) to form a sealed cavity between the cover plate (5) and the water guide table (22); the sewage degradation assembly (3) and the photocatalytic hydrogen production assembly (4) are both arranged in the sealed cavity, and a light-transmitting window (52) is arranged on the cover plate (5); an exhaust hole (51) for discharging the produced hydrogen is further arranged on the cover plate (5) and / or the water guide table (22).

8. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 7, characterized in that, A plurality of the water guide tables (22) are evenly distributed at intervals on the outer periphery of the top of the installation base (21). The sewage degradation assembly (3) and the photocatalytic hydrogen production assembly (4) are sequentially arranged from high to low on the water guide surface of any one of the water guide tables (22), and the cover plate (5) is arranged on any one of the water guide tables (22).

9. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 8, wherein, The installation base (21) is a cuboid base, and one end in the height direction of the cuboid base is inserted into the port of the water storage cavity (11); the water guide table (22) is a rectangular water guide table, and two of the rectangular water guide tables are symmetrically arranged at the other end in the height direction of the cuboid base, and the two rectangular water guide tables are respectively located on both sides in the width direction of the cuboid base; the included angle α between the axis in the length direction of any one of the rectangular water guide tables and the axis in the height direction of the cuboid base is 35° to 85°; The cover plate (5) is a rectangular cover plate, and the length L1 of the rectangular cover plate is equal to the length L2 of the rectangular water guide table; the length L2 of the rectangular water guide table is greater than the width L3 of the cuboid base.

10. The sewage degradation and photocatalytic hydrogen production coupling device according to claim 7, wherein A light-transmitting opening (53) is formed in the cover plate (5), and a glass plate (54) is embedded in the light-transmitting opening (53) to form the light-transmitting window (52).

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