Interface type photo-thermal synergistic hydrogen production reactor

Abstract

The invention discloses an interface type photo-thermal synergistic hydrogen production reactor which comprises a shell and a hydrogen production reaction structure. The shell is provided with a feeding port, the hydrogen production reaction structure is arranged in the shell, and a gas channel is formed between the hydrogen production reaction structure and the shell. An internal channel is formed in the hydrogen production reaction structure in the axial direction of the hydrogen production reaction structure, the internal channel is communicated with the feeding port, at least part of the hydrogen production reaction structure is of a porous structure, and the porous structure is provided with a catalyst for hydrogen production. A reaction solution enters the internal channel through the feeding port and radially diffuses to the surface of the hydrogen production reaction structure from the porous structure, and gas generated by the reaction solution through a catalytic reaction is discharged from the gas channel. The interface type photo-thermal synergistic hydrogen production reactor combines photo-thermal catalysis and thermocatalysis effects, utilizes solar energy to the maximum extent, adopts brand new radial conveying, and has the advantages that the flowing speeds of reaction solutions at all positions in the radial direction are consistent, and the reaction is more uniform and more sufficient.

Description

Technical Field

[0001] The present invention relates to the technical field of renewable energy utilization, and in particular to an interfacial photothermal synergistic hydrogen production reactor. Background Art

[0002] Solar energy resources on Earth are very abundant, and are widely distributed, easy to develop, and environmentally friendly. Currently, the use of solar energy includes solar thermal power generation and photovoltaic power generation. Directly converting sunlight into chemical energy using chemical conversion methods is an emerging method in recent years, such as converting solar energy into hydrogen energy.

[0003] Common solar hydrogen production methods mainly include solar photocatalytic hydrogen production and solar thermochemical hydrogen production. At present, in most photocatalytic hydrogen production reactors, powdered photocatalysts are dispersed in the reaction liquid in a suspended form to form a suspended reactor. This mode can ensure sufficient contact between the catalyst and the reactants, but the catalyst is easily agglomerated when suspended in the solution for a long time, which reduces the hydrogen production performance. When the powdered photocatalyst is dispersed in the solution, the transmission of light in the entire reaction system is easily limited. As the thickness / depth of the solution increases, the light attenuation becomes extremely serious. In addition, common photocatalytic hydrogen production reactors only use the short-wave part of the solar spectrum for oxidation-reduction hydrogen production, the utilization rate of the solar spectrum is low, and the hydrogen production efficiency is relatively low.

[0004] At present, most photothermal catalytic hydrogen production reactors use the spectral absorption capacity of heat-collecting materials such as Cr film, Cu-Al-SS, Bi2Te3 / Cu in visible light and near-infrared light and the photothermal effect to heat the reaction system, so that its temperature rises to the starting temperature of the thermal catalytic reaction, and hydrogen is produced through the thermal catalytic reaction. This hydrogen production method is called PDTC (Photo-driven Thermal Catalytic). This method is actually still thermal catalytic hydrogen production, and does not fully utilize the high-energy short-wave part of the solar spectrum. In addition, the structure of the reactor and the filling method of the catalyst lead to the disadvantages of uneven reaction, insufficient catalyst utilization, and large flow resistance. In addition, the reaction solution flows in the axial direction in the reactor, and the catalytic reaction does not occur in the entire section. The solar energy in the latter section is only used to heat the unreacted water vapor and the generated gas, so the catalyst is not effectively utilized, and the high-energy part of the solar energy cannot be added to the reaction system during the entire process. Summary of the invention

[0005] Based on this, it is necessary to provide an interfacial photothermal synergistic hydrogen production reactor to address the problems of low solar spectrum utilization, low catalyst utilization, and relatively low hydrogen production efficiency in existing solar photocatalytic hydrogen production and solar thermochemical hydrogen production.

[0006] An interfacial photothermal synergistic hydrogen production reactor, comprising:

[0007] A housing, wherein the housing is provided with a feed inlet; and

[0008] A hydrogen production reaction structure is arranged in the shell, a gas channel is formed between the hydrogen production reaction structure and the shell, an internal channel is arranged in the hydrogen production reaction structure along its axial direction, the internal channel is communicated with the feed inlet, and the hydrogen production reaction structure is at least partially a porous structure, and the porous structure is provided with a catalyst for producing hydrogen;

[0009] The reaction solution enters the internal channel through the feed port, diffuses radially from the porous structure to the surface of the hydrogen production reaction structure, and the gas generated by the catalytic reaction of the reaction solution is discharged from the gas channel.

[0010] In the above-mentioned interfacial photothermal synergistic hydrogen production reactor, the reaction solution enters the internal channel of the hydrogen production reaction structure from the feed port. After entering the internal channel, the reaction solution diffuses radially from the porous structure. Since the surface area of ​​the hydrogen production reaction structure is much larger than its cross-sectional area, the radial flow velocity of the reaction solution will be greatly reduced, and the reaction will be more complete during the process of flowing through the porous structure. During the radial flow of the reaction solution, it will participate in the catalytic reaction in the form of steam to produce hydrogen, and the conversion rate will be improved. Finally, the incompletely reacted steam and the generated gas are discharged through the gas channel and recovered by the condensing device.

[0011] In one of the embodiments, the porous structure includes a reaction unit layer, the catalyst for producing hydrogen includes a photothermal catalyst and a thermal catalyst, and the photothermal catalyst and the thermal catalyst together constitute the reaction unit layer.

[0012] In one of the embodiments, the side wall of the porous structure further includes a photothermal conversion unit layer, and the photothermal conversion unit layer is arranged inside the reaction unit layer.

[0013] In one of the embodiments, the porous structure further includes a transport unit layer, and the transport unit layer is arranged on the inner side of the light-to-heat conversion unit layer.

[0014] In one of the embodiments, the porous structure further includes a heat insulation unit layer, and the heat insulation unit layer is arranged between the light-to-heat conversion unit layer and the transport unit layer.

[0015] In one of the embodiments, a support member is further included, and the support member is disposed in the internal channel to support the hydrogen production reaction structure.

[0016] In one of the embodiments, a baffle is further included, wherein the baffle is installed at the end of the support member, and the baffle is used to close the port of the internal channel away from the feed port.

[0017] In one embodiment, the shell includes an outer shell and an inner shell disposed in the outer shell, the outer shell and the inner shell are light-transmissive, and a vacuum is provided between the outer shell and the inner shell.

[0018] In one of the embodiments, a concentrator is further included, and the concentrator is arranged outside the shell and is used to focus sunlight to heat the reaction solution.

[0019] In one of the embodiments, the hydrogen production reaction structure is coaxially arranged with the shell.

[0020] The above-mentioned interfacial photothermal synergistic hydrogen production reactor combines the effects of photothermal catalysis and thermal catalysis to effectively utilize the full spectrum of solar energy, thereby achieving efficient hydrogen production. Abandoning the traditional axial transportation method of the reaction solution in the reactor, a new radial transportation method is adopted. The advantage is that the flow rate of the reaction solution in each radial direction is consistent, the reaction is more uniform and more complete, and the higher energy part of the solar energy spectrum can be added to the reaction system. The reactor can maximize the use of solar energy. The shorter wavelength part can be used for photochemical reactions in photothermal catalytic reactions and to reduce the temperature of thermochemical reactions. The longer wavelength part can achieve photothermal conversion through the photothermal effect to increase the temperature and achieve thermal catalytic hydrogen production. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the specific implementation of the present invention, the following will briefly introduce the drawings required for use in the specific implementation. In all the drawings, each element or part is not necessarily drawn according to the actual scale.

[0022] Figure 1 This is a schematic structural diagram of an interfacial photothermal synergistic hydrogen production reactor in one embodiment;

[0023] Figure 2 for Figure 1 A schematic diagram of the structure of the middle shell;

[0024] Figure 3 for Figure 1 A cross-sectional view of an interfacial photothermal synergistic hydrogen production reactor is shown;

[0025] Figure 4 for Figure 1 A cross-sectional view of an interfacial photothermal synergistic hydrogen production reactor is shown;

[0026] Figure 5 for Figure 3 Schematic diagram of the side wall multilayer structure of the hydrogen production reaction structure;

[0027] Figure 6 for Figure 3 Schematic diagram of the structure of the middle support.

[0028] Reference numerals:

[0029] 1-sunlight, 10-shell, 11-feed port, 12-gas channel, 13-outer shell, 14-inner shell, 20-hydrogen production reaction structure, 201-internal channel, 202-porous structure, 21-reaction unit layer, 22-photothermal conversion unit layer, 23-transport unit layer, 24-insulation unit layer, 30-concentrator, 40-support, 41-baffle, 50-connecting shell. DETAILED DESCRIPTION

[0030] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the invention is not limited by the specific implementation disclosed below.

[0031] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly on the other element or there may be a central element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be a central element at the same time. The terms "vertical", "horizontal", "left", "right" and similar expressions used herein are for illustrative purposes only and do not represent the only implementation method.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0033] See also Figure 1 In one embodiment, an interfacial photothermal hydrogen production reactor includes a shell 10 and a hydrogen production reaction structure 20.

[0034] The shell 10 is used to accommodate the hydrogen production reaction structure 20 , and the shell 10 is generally a cylindrical structure. The shell 10 is a transparent pipe so that the external sunlight 1 can irradiate the hydrogen production reaction structure 20 .

[0035] Please also read Figure 2In one embodiment, the shell 10 includes an outer shell 13 and an inner shell 14 disposed in the outer shell 13, the outer shell 13 and the inner shell 14 are light-transmissive, and a vacuum is set between the outer shell 13 and the inner shell 14. The vacuum design between the outer shell 13 and the inner shell 14 allows the shell 10 to be heat-insulated and heat-preserved, thereby reducing heat loss in the shell 10 and ensuring the hydrogen production process. Specifically, the outer shell 13 and the inner shell 14 can be made of glass, transparent quartz glass, etc.

[0036] Please also read Figure 3 and Figure 4 The shell 10 is provided with a feed inlet 11, the hydrogen production reaction structure 20 is generally cylindrical, and the hydrogen production reaction structure 20 is arranged in the shell 10, and a gas channel 12 is formed between the hydrogen production reaction structure 20 and the shell 10. The hydrogen production reaction structure 20 is provided with an internal channel 201 extending along its axial direction, and the internal channel 201 is connected with the feed inlet 11, and the external reaction solution can enter the internal channel 201 from the feed inlet 11.

[0037] Specifically, the hydrogen production reaction structure 20 has a first end and a second end relative to each other. The hydrogen production reaction structure 20 is connected to the feed port 11 at the first end. The internal channel 201 extends from the first end to the second end along the axial direction of the hydrogen production reaction structure 20. The second end closes the port of the internal channel 201 to prevent the reaction solution from flowing out axially.

[0038] The hydrogen production reaction structure 20 is at least partially a porous structure 202, and the porous structure 202 is provided with a catalyst for producing hydrogen. After the reaction solution enters the internal channel 201 through the feed port 11, the reaction solution diffuses radially from the porous structure 202 to the surface of the hydrogen production reaction structure 20. Since the surface area of ​​the hydrogen production reaction structure 20 is much larger than its cross-sectional area, the radial flow velocity of the reaction solution will be greatly reduced, and the reaction will be more complete during the process of flowing through the porous structure 202. During the radial flow of the reaction solution, it will participate in the catalytic reaction in the form of steam to produce hydrogen, and the conversion rate will be improved. Finally, the unreacted steam and the generated gas are discharged through the gas channel 12 and recovered by the condensing device.

[0039] In one embodiment, the reaction solution may be pure water, a mixed solution of organic matter and water, or pure organic matter, etc., which may be specifically selected according to actual needs.

[0040] In one embodiment, the hydrogen production reaction structure 20 is coaxially arranged with the shell 10, and the hydrogen production reaction structure 20 is located in the center of the shell 10, which can ensure that the hydrogen production reaction structure 20 is evenly exposed to sunlight 1 and heat, and ensure that the hydrogen production reaction process is sufficient and uniform.

[0041] In one embodiment, the area of ​​the hydrogen production reaction structure 20 covered by the shell 10 is a porous structure 202 to ensure the fullness and efficiency of the hydrogen production reaction and maximize the use of solar energy. It is understandable that in other embodiments, the porous structure 202 area of ​​the hydrogen production reaction structure 20 can be specifically selected according to actual needs, such as the length of the porous structure 202 is shorter than the area covered by the shell 10, or the length of the porous structure 202 is longer than the area covered by the shell 10, or the hydrogen production reaction structure 20 is entirely a porous structure 202.

[0042] In one embodiment, the interfacial photothermal synergistic hydrogen production reactor further includes a concentrator 30, which is disposed outside the housing 10 and is used to collect sunlight 1 to heat the reaction solution in the housing 10. In one embodiment, the sunlight 1 can be continuous irradiation sunlight 1 or discontinuous irradiation sunlight 1. Preferably, it is continuous irradiation sunlight 1. Due to the non-uniformity of sunlight 1, the concentration ratio of the concentrator 30 can be reasonably adjusted to achieve the optimal operating light intensity and temperature of the hydrogen production reaction.

[0043] In one embodiment, considering the changes in the incident angles of different sunlight 1 in the actual environment, the concentrator 30 provided by the present invention is equipped with a light tracking system to track the changes in the incident angles of different sunlight 1. The specific structure of the light tracking system adopts the existing light tracking system and is not described in detail here.

[0044] Please also read Figure 5 In one embodiment, the porous structure 202 includes a reaction unit layer 21, and the catalyst for hydrogen production includes a photothermal catalyst and a thermal catalyst, which together constitute the reaction unit layer 21. The reaction unit layer 21 is heated to a thermal catalytic starting temperature by the full spectrum absorption of the photothermal catalyst, thereby causing a thermal catalytic reaction, and simultaneously performing photothermal synergistic catalysis, thereby realizing efficient hydrogen production using the full spectrum of solar energy.

[0045] In one embodiment, the photothermal catalyst uses materials such as PPCN, Pt-TiO2 and CuO. The thermal catalyst uses materials such as CuO / ZnO / Al2O3, CeO2 and MnOX. The thickness of the reaction unit layer 21 is specifically selected according to the size of the reactor and the hydrogen production demand.

[0046] In one embodiment, the reaction unit layer 21 is prepared by a template method, and the preparation process is specifically as follows:

[0047] The commercial white sugar particles are placed in an oven to be fully dried at an oven temperature of 60°C to 80°C and a drying time of 4 to 5 hours. A certain mass of photothermal catalyst and thermal catalyst are mixed with a certain amount of PVA (polyvinyl alcohol) solution and magnetically stirred for 4 to 6 hours. The dried sugar particles are placed in a template, evenly dispersed by extrusion, and then a mixed solution of photothermal catalyst and thermal catalyst is injected, and the catalyst solution is infiltrated into the sugar particles by capillary action. After the infiltrated sugar particles are placed in a drying oven for a certain period of time, the solvent is volatilized, the drying temperature is 50 to 70°C, and the drying time is 10 to 12 hours, and a dry catalyst porous structure 202 with sugar particles is obtained. Finally, the porous structure 202 is placed in deionized water to remove the template, i.e., the sugar particles, and after drying, a catalytic material composited with a photothermal catalyst and a thermal catalyst having a porous structure 202 can be obtained.

[0048] In one embodiment, the porous structure 202 further includes a photothermal conversion unit layer 22, which is disposed inside the reaction unit layer 21. The photothermal conversion unit layer 22 converts sunlight 1 into thermal energy through the photothermal effect, thereby ensuring the temperature of the thermal catalytic reaction. Specifically, the photothermal conversion unit layer 22 is generally made of photothermal conversion materials such as Cr film, Cu-Al-SS, Bi2Te3 / Cu, TiN, graphite, and carbon nanotubes. The preparation method of the photothermal conversion unit layer 22 is similar to that of the reaction unit layer 21, except that the catalyst is replaced with a photothermal conversion material.

[0049] In one embodiment, the porous structure 202 further includes a transport unit layer 23, which is disposed on the inner side of the photothermal conversion unit layer 22, and is used to transport the reaction solution to the photothermal conversion unit layer 22. Specifically, the transport unit layer 23 is a 3D printed porous material, and the superheated steam enters the photothermal conversion unit layer 22 through the porous material layer, and finally enters the reaction unit layer 21, and obtains hydrogen through photothermal catalysis and thermal catalysis reactions.

[0050] In one embodiment, in order to ensure that the photothermal conversion unit layer 22 transfers the heat converted from solar energy to the reaction unit layer 21, the porous structure 202 further includes a heat insulation unit layer 24, which is arranged between the photothermal conversion unit layer 22 and the transport unit layer 23. The heat insulation unit layer 24 prevents heat from diffusing to the transport unit layer 23, effectively maintaining the temperature of the reaction unit layer 21. This layer generally uses renewable natural-based materials such as cotton stalk fiber, flax and cellulose fiber, and can also use thermal insulation materials such as asbestos, glass fiber, polystyrene foam, etc.

[0051] Please also read Figure 3 and Figure 6In one embodiment, the interfacial photothermal hydrogen production reactor further includes a support member 40 , which is generally a long strip structure. The support member 40 is disposed in the internal channel 201 to support the hydrogen production reaction structure 20 .

[0052] Since the hydrogen production reaction structure 20 includes a porous structure 202 that is prone to bending, the support member 40 can support the hydrogen production reaction structure 20 to prevent the hydrogen production reaction structure 20 from bending. In order to reduce the overall weight of the reactor, the support member 40 is made of a thin-walled metal material. At the same time, in order not to hinder the flow of the reaction solution in the internal channel 201, the support member 40 can be a cross or a cross shape.

[0053] On the basis of the above embodiments, the interfacial photothermal hydrogen production reactor further includes a baffle 41, which is installed at the end of the support 40. The baffle 41 is used to close the port of the internal channel 201 away from the feed inlet 11, so that the second end closes the port of the internal channel 201 to prevent the reaction solution from flowing out axially.

[0054] Please refer again Figure 1 In one embodiment, the interfacial photothermal synergistic hydrogen production reactor further includes a connecting shell 50, which is installed at the end of the shell 10 away from the feed inlet 11. The space between the connecting shell 50 and the hydrogen production reaction structure 20 is used to discharge hydrogen and unreacted reaction solution. Specifically, the connecting shell 50 is a single-layer glass round tube, and the material and size of the connecting shell 50 are the same as those of the outer shell 13.

[0055] The working principle of the above-mentioned interfacial photothermal synergistic hydrogen production reactor is as follows:

[0056] The reaction solution enters the internal channel 201 from the feed port 11 of the shell 10, and the hydrogen production reaction structure 20 is coated on the outside of the support 40. After entering the internal channel 201, the reaction solution diffuses radially from the porous structure 202. Since the surface area of ​​the hydrogen production reaction structure 20 is much larger than the cross-sectional area of ​​the hydrogen production reaction structure 20, the radial flow velocity of the reaction solution will be greatly reduced, and the reaction will be more sufficient in the process of flowing through the porous structure 202.

[0057] The reaction solution passes through the transport unit layer 23 and enters the heat insulation unit layer 24, then enters the photothermal conversion unit layer 22, and finally enters the reaction unit layer 21. Since the temperature of the reaction unit layer 21 and the photothermal conversion unit layer 22 is relatively high (150°C to 260°C), when the reaction solution is transferred to the outermost layer of the porous structure 202, i.e., the reaction unit layer 21, it will participate in the photothermal synergistic catalytic reaction and the thermal catalytic reaction in the form of steam, and the conversion rate will be improved. Finally, the unreacted steam and the generated gas are discharged from the reaction device through the gas channel 12 formed by the shell 10 and the hydrogen production reaction structure 20, and are recovered through the condensation device.

[0058] The above-mentioned interfacial photothermal synergistic hydrogen production reactor abandons the traditional suspended photocatalytic reaction method, adopts an interfacial reaction system, combines the effects of photothermal catalysis and thermal catalysis, and effectively utilizes the full spectrum of solar energy to achieve efficient hydrogen production. Abandoning the traditional axial transportation method of the reaction solution in the reactor, a new radial transportation method is adopted. Its advantage is that the flow rate of the reaction solution in each radial direction is consistent, the reaction is more uniform and more complete, and the higher energy part of the solar energy spectrum can be added to the reaction system. The reactor can maximize the use of solar energy. The shorter wavelength part can be used for photochemical reactions in photothermal catalytic reactions and reduce the temperature of thermochemical reactions. The longer wavelength part can realize photothermal conversion through the photothermal effect to increase the temperature and realize thermal catalytic hydrogen production.

[0059] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

Claims

1. An interfacial photothermal synergistic hydrogen production reactor, characterized in that: include: A shell body, wherein the shell body is provided with a feed inlet; and A hydrogen production reaction structure is arranged in the shell, a gas channel is formed between the hydrogen production reaction structure and the shell, an internal channel is arranged in the hydrogen production reaction structure along its axial direction, the internal channel is communicated with the feed inlet, and the hydrogen production reaction structure is at least partially a porous structure, and the porous structure is provided with a catalyst for producing hydrogen; The reaction solution enters the internal channel through the feed port, diffuses radially from the porous structure to the surface of the hydrogen production reaction structure, and the gas generated by the catalytic reaction of the reaction solution is discharged from the gas channel.

2. The interfacial photothermal hydrogen production reactor according to claim 1, characterized in that: The porous structure includes a reaction unit layer, and the catalyst for producing hydrogen includes a photothermal catalyst and a thermal catalyst, and the photothermal catalyst and the thermal catalyst together constitute the reaction unit layer.

3. The interfacial photothermal hydrogen production reactor according to claim 2, characterized in that: The side wall of the porous structure further includes a photothermal conversion unit layer, and the photothermal conversion unit layer is arranged inside the reaction unit layer.

4. The interfacial photothermal hydrogen production reactor according to claim 3 is characterized in that: The porous structure further includes a transport unit layer, and the transport unit layer is arranged on the inner side of the light-to-heat conversion unit layer.

5. The interfacial photothermal synergistic hydrogen production reactor according to claim 4, characterized in that: The porous structure further includes a heat insulation unit layer, and the heat insulation unit layer is arranged between the light-to-heat conversion unit layer and the transport unit layer.

6. The interfacial photothermal hydrogen production reactor according to claim 1, characterized in that: It also includes a support member, which is arranged in the internal channel to support the hydrogen production reaction structure.

7. The interfacial photothermal hydrogen production reactor according to claim 6, characterized in that: It also includes a baffle, which is installed at the end of the support member and is used to close the port of the internal channel away from the feed inlet.

8. The interfacial photothermal hydrogen production reactor according to claim 1, characterized in that: The shell comprises an outer shell and an inner shell arranged in the outer shell, the outer shell and the inner shell are light-transmissive, and a vacuum is arranged between the outer shell and the inner shell.

9. The interfacial photothermal synergistic hydrogen production reactor according to claim 1, characterized in that: It also includes a concentrator, which is arranged outside the shell and is used to focus sunlight to heat the reaction solution.

10. The interfacial photothermal hydrogen production reactor according to claim 1, characterized in that: The hydrogen production reaction structure is coaxially arranged with the shell.

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