Three-dimensional porous difunctional photo-biomass hydrogen production membrane electrode device

Abstract

The invention relates to the technical field of new energy materials and hydrogen energy, in particular to a three-dimensional porous difunctional photo-biomass hydrogen production membrane electrode device which comprises a transparent cover body, a bottom cover assembly is installed at the other end of the transparent cover body through a bolt and comprises a shell, grouting pipes are welded to the outer walls of the two sides of the top of the shell, and the grouting pipes are connected with the transparent cover body through bolts. One end of the grouting pipe is in threaded connection with a pipe cover. The bottom cover assembly further comprises a first photocatalysis plate, a first conversion plate, a proton exchange plate, a second photocatalysis plate and a second conversion plate. A three-dimensional porous channel is formed through the cavity channels and the through holes in the substrate, the electrolyte permeation efficiency is greatly improved, meanwhile, the bubble retention risk is reduced, the mass transfer kinetics of photocatalysis and biomass reaction is remarkably optimized, and due to the alternate arrangement design of the first photocatalysis plate, the first conversion plate, the proton exchange plate and other assemblies, the photocatalytic efficiency is greatly improved. Space decoupling of photocatalytic hydrogen production and biomass electron transfer is achieved, cross interference of reaction paths is avoided, and the total energy conversion efficiency is greatly improved.

Description

Technical Field

[0001] The present invention relates to the technical field of new energy materials and hydrogen energy technology, and particularly relates to a three-dimensional porous bifunctional photo-biomass hydrogen production membrane electrode device. Background Art

[0002] Biomass membrane electrode hydrogen production is a green hydrogen production technology that combines biomass raw material conversion and membrane electrode electrochemical reactions. By integrating biomass resource utilization and proton exchange membrane (PEM) technology, efficient and low-carbon hydrogen production can be achieved.

[0003] For example, a bipolar plate for electrolytic water hydrogen production with the application number CN202323667996.5 and the authorization announcement date of 20241206 includes: a pole frame and a bipolar plate body. The pole frame is arranged on the outer peripheral side of the bipolar plate body, and the pole frame and the bipolar plate body are of an integral structure; a plurality of flow channels are opened on both opposite side surfaces of the bipolar plate body. The plurality of flow channels are of a "Λ"-shaped three-dimensional structure, and the plurality of flow channels face the same direction and are non-uniformly symmetrically distributed. The bipolar plate for electrolytic water hydrogen production of the present utility model improves the disturbance degree of the electrolyte and gas flowing through the bipolar plate body by designing the "Λ"-shaped three-dimensional structure flow channels, reduces the electrolyte concentration difference and gas concentration difference at each part in the flow channels, makes the electrolyte and gas distribution more uniform, not only improves the efficiency of electrolytic water hydrogen production, but also has a lower loss to the electrolytic cell, improves the service life of the electrolytic cell, and is beneficial to the long-term stable operation of the electrolytic cell.

[0004] Traditional hydrogen production devices mostly adopt a single hydrogen production path (photocatalysis or electrolytic water), and do not achieve the bifunctional coordination of photocatalysis and biomass conversion. The energy conversion efficiency is generally lower than 60%, and the planar electrode design results in a low electrolyte penetration rate (≤20 mL / (cm 2 ·min)), and serious bubble retention. Therefore, it is urgent to design a three-dimensional porous bifunctional photo-biomass hydrogen production membrane electrode device to solve the above problems. Summary of the Invention

[0005] The purpose of the present invention is to provide a three-dimensional porous bifunctional photo-biomass hydrogen production membrane electrode device to solve the above deficiencies in the prior art.

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

[0007] A three-dimensional porous bifunctional photo-biomass hydrogen production membrane electrode device, comprising a transparent cover body, the other end of the transparent cover body is installed with a bottom cover assembly through bolts, the bottom cover assembly includes a housing, both outer walls on both sides of the top of the housing are welded with grouting pipes, and one end of the grouting pipe is threadedly connected with a pipe cap, the bottom cover assembly further includes a first photocatalytic plate, a first conversion plate, a proton exchange plate, a second photocatalytic plate and a second conversion plate, the first photocatalytic plate, the first conversion plate, the proton exchange plate, the second photocatalytic plate and the second conversion plate are all welded on the outer wall of one side of the bottom of the housing, the first photocatalytic plate, the first conversion plate, the proton exchange plate, the second photocatalytic plate and the second conversion plate are distributed in sequence from front to back, the first photocatalytic plate, the first conversion plate, the proton exchange plate, the second photocatalytic plate and the second conversion plate all include a substrate, a cavity is opened on the top of the substrate, and the cavity communicates with the housing, a plurality of embedding grooves are opened on one outer wall of the substrate, and filling blocks are embedded in the embedding grooves, and a plurality of through holes are opened on the inner wall of the embedding grooves, and the through holes communicate with the cavity.

[0008] Further, a groove is opened on the outside of the transparent cover body, and a light strip board is wound in the groove.

[0009] Further, a top cover is installed on one end of the transparent cover body through bolts, and a hydrogen outlet pipe and an exhaust pipe are respectively inserted on both outer walls of the top of the top cover, and electrode seats are installed on both outer walls of the top of the top cover through bolts.

[0010] Further, two grid plates are installed in the transparent cover body through bolts, and the grid plates are electrically connected to the electrode seats through wires.

[0011] Further, an installation groove is opened on one end of the transparent cover body, and the housing is installed in the installation groove through bolts.

[0012] Further, the filling blocks on the first photocatalytic plate and the second photocatalytic plate are honeycomb-shaped photocatalytic nanosheets, the filling blocks on the first conversion plate and the second conversion plate are honeycomb-shaped biomass conversion catalysts, and the filling blocks on the proton exchange plate are proton exchange membranes.

[0013] Further, a flow disturbing component is installed on one outer wall of the top of the housing through bolts, the flow disturbing component includes a pump body, the pump body is installed at the center of the top of the housing through bolts, a liquid suction pipe is inserted at the feeding end of the pump body, and the liquid suction pipe extends into the transparent cover body.

[0014] Further, a first filter box and a second filter box are respectively installed on both outer walls of the pump body through bolts, and the first filter box and the second filter box are communicated with the discharging end of the pump body through pipelines.

[0015] Furthermore, on one side of the top outer wall of each of the first filtration tank and the second filtration tank, a placement groove is provided, and a cover plate is installed inside the placement groove through bolts. On one side of the bottom outer wall of the cover plate, a filter element is installed through bolts.

[0016] Furthermore, on one side outer wall of each of the first filtration tank and the second filtration tank, a connecting pipe is inserted. On both sides of the bottom outer wall of the connecting pipe, a plurality of return pipes are inserted. The two groups of return pipes are respectively located between the first photocatalytic plate and the first conversion plate, and between the second photocatalytic plate and the second conversion plate.

[0017] In the above technical solution, for a three-dimensional porous dual-functional photo-biomass hydrogen production membrane electrode device provided by the present invention, the beneficial effects are as follows:

[0018] (1) In the present invention, a three-dimensional porous channel is formed by the channels and through holes on the substrate, which greatly improves the electrolyte penetration efficiency, reduces the risk of bubble retention at the same time, significantly optimizes the mass transfer kinetics of photocatalysis and biomass reactions, and the alternating arrangement design of components such as the first photocatalytic plate, the first conversion plate, and the proton exchange plate realizes the spatial decoupling of photocatalytic hydrogen production and biomass electron transfer, avoiding cross-interference of reaction paths, and greatly improving the total energy conversion efficiency.

[0019] (2) In the present invention, the pump body forms a dynamic circulation of the electrolyte through the liquid extraction pipe and the return pipe. Combined with the filter elements in the first filtration tank and the second filtration tank, it effectively intercepts biomass residues and precipitates, intercepts impurities and maintains the activity of the catalyst, greatly extends the continuous operation period of the device, and the turbulence generating component enhances the turbulent effect in the pores through jet impact, and the conversion rate of biomass raw materials is greatly improved.

[0020] (3) In the present invention, through the grouting pipe, not only can new electrolyte slurry be injected into the shell, but also the filling blocks on the substrate can be backwashed by injecting clean water, avoiding the influence of impurities accumulating on the filling blocks during the long reaction time of the device on subsequent catalytic reactions. Description of the Drawings

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required in the embodiments. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings.

[0022] Figure 1 It is a schematic diagram of the overall structure provided by an embodiment of a three-dimensional porous dual-functional photo-biomass hydrogen production membrane electrode device of the present invention.

[0023] Figure 2 It is a schematic diagram of the transparent cover, bottom cover assembly and top cover structure provided by an embodiment of a three-dimensional porous dual-functional photo-biomass hydrogen production membrane electrode device of the present invention.

[0024] Figure 3 Schematic diagram of the transparent cover, top cover, and grid electrode plate structure provided for an embodiment of a three-dimensional porous dual-functional photocatalytic biomass hydrogen production membrane electrode device of the present invention.

[0025] Figure 4 Schematic diagram of the bottom cover assembly structure provided for an embodiment of a three-dimensional porous dual-functional photocatalytic biomass hydrogen production membrane electrode device of the present invention.

[0026] Figure 5 Provided for an embodiment of a three-dimensional porous dual-functional photocatalytic biomass hydrogen production membrane electrode device of the present invention Figure 4 Enlarged structure diagram of part A in

[0027] Figure 6 Schematic diagram of the flow disturbance assembly structure provided for an embodiment of a three-dimensional porous dual-functional photocatalytic biomass hydrogen production membrane electrode device of the present invention.

[0028] Description of reference numerals:

[0029] 1. Transparent cover; 2. Bottom cover assembly; 3. Top cover; 4. Groove; 5. Light strip board; 6. Hydrogen outlet pipe; 7. Electrode seat; 8. Exhaust pipe; 9. Installation groove; 10. Grid electrode plate; 11. Shell; 12. Grouting pipe; 13. Pipe cover; 14. Flow disturbance assembly; 15. First photocatalytic plate; 16. First conversion plate; 17. Proton exchange plate; 18. Second photocatalytic plate; 19. Second conversion plate; 20. Substrate; 21. Channel; 22. Embedding groove; 23. Through hole; 24. Filling block; 25. First filter box; 26. Second filter box; 27. Pump body; 28. Placement groove; 29. Connecting pipe; 30. Return pipe; 31. Cover plate; 32. Filter element; 33. Liquid extraction pipe. Detailed implementation manners

[0030] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further introduced in detail below with reference to the accompanying drawings.

[0031] As Figures 1-6As shown in the figure, a three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device provided by an embodiment of the present invention includes a transparent cover body 1. The other end of the transparent cover body 1 is installed with a bottom cover assembly 2 through bolts. The bottom cover assembly 2 includes a housing 11. Both outer walls on two sides of the top of the housing 11 are welded with grouting pipes 12. Through the grouting pipes 12, not only can new electrolyte slurry be injected into the interior of the housing 11, but also the filling blocks 24 on the substrate 20 can be backwashed by injecting clean water, so as to avoid the filling blocks 24 being filled with impurities after a long reaction time of the device, which affects subsequent catalytic reactions. One end of the grouting pipe 12 is threadedly connected with a pipe cap 13. The bottom cover assembly 2 further includes a first photocatalytic plate 15, a first conversion plate 16, a proton exchange plate 17, a second photocatalytic plate 18 and a second conversion plate 19. During photocatalytic hydrogen production, the light strip board 5 outside the transparent cover body 1 will emit multi-band light of 400-700 nm, exciting the honeycomb photocatalytic nanosheets on the first photocatalytic plate 15 and the second photocatalytic plate 18. Photo-generated electrons jump from the valence band to the conduction band and contact with electrolyte water or biomass-containing wastewater in the channel 21 of the substrate 20 to decompose water to produce hydrogen. During subsequent biomass electron conversion, the honeycomb catalysts of the first conversion plate 16 and the second conversion plate 19 will adsorb organic substances in the wastewater and release electrons through enzymatic catalytic reactions. The biomass electrons are transmitted to the proton exchange plate 17 through the through holes 23 in the embedding grooves 22 and participate in the hydrogen production reaction synergistically with the photo-generated electrons. As the reaction proceeds, mass transfer and proton exchange will occur, and a multi-stage penetration network is formed by the channel 21 and the through holes 23 of the substrate 20. After the electrolyte is injected into the housing 11 through the grouting pipe 12, it quickly diffuses to each layer plate along the channel 21. With the synergistic effect of the micron-scale channel 21 and the nano-scale through holes 23, the electrolyte penetration rate will be greatly improved. The first photocatalytic plate 15, the first conversion plate 16, the proton exchange plate 17, the second photocatalytic plate 18 and the second conversion plate 19 are all welded on the outer wall of one side of the bottom of the housing 11, and the first photocatalytic plate 15, the first conversion plate 16, the proton exchange plate 17, the second photocatalytic plate 18 and the second conversion plate 19 are distributed in sequence from front to back. The first photocatalytic plate 15, the first conversion plate 16, the proton exchange plate 17, the second photocatalytic plate 18 and the second conversion plate 19 all include a substrate 20. A channel 21 is opened at the top of the substrate 20, and the channel 21 communicates with the housing 11. A plurality of embedding grooves 22 are opened on one outer wall of the substrate 20, and filling blocks 24 are embedded inside the embedding grooves 22. A plurality of through holes 23 are opened on the inner wall of the embedding grooves 22, and the through holes 23 communicate with the channel 21. The filling blocks 24 on the first photocatalytic plate 15 and the second photocatalytic plate 18 are honeycomb photocatalytic nanosheets, and are preferably titanium dioxide-based composite materials. The filling blocks 24 on the first conversion plate 16 and the second conversion plate 19 are honeycomb biomass conversion catalysts, and are preferably Pyrococcus furiosus hydrogenase, loaded on an activated carbon honeycomb carrier. The filling blocks 24 on the proton exchange plate 17 are proton exchange membranes, and are preferably composite reinforced membranes.

[0032] In one embodiment provided by the present invention, asFigures 1-3 As shown, a groove 4 is provided on the outside of the transparent cover body 1, and a lamp strip board 5 is wound inside the groove 4. The lamp strip board 5 is preferably a multi-band LED light source. When photocatalytic hydrogen production occurs, the lamp strip board 5 outside the transparent cover body 1 will emit multi-band light of 400-700 nm, exciting the honeycomb photocatalytic nanosheets on the photocatalytic plate one 15 and the photocatalytic plate two 18. One end of the transparent cover body 1 is installed with a top cover 3 through bolts, and hydrogen outlet pipes 6 and exhaust pipes 8 are respectively inserted on both outer walls of the top of the top cover 3. Electrode seats 7 are installed on both outer walls of the top of the top cover 3 through bolts. Two grid electrode plates 10 are installed inside the transparent cover body 1 through bolts. The electrode seats 7 and the grid electrode plates 10 are preferably two types of titanium-based coated electrodes and graphene composite electrodes. The electrode seats 7 and the grid electrode plates 10 are connected together. When the two groups of electrode seats 7 and the grid electrode plates 10 are energized, they will become the anode and the cathode, and the grid electrode plates 10 are electrically connected to the electrode seats 7 through wires. An installation groove 9 is provided at one end of the transparent cover body 1, and the housing 11 is installed inside the installation groove 9 through bolts.

[0033] In another embodiment provided by the present invention, as Figure 4 and Figure 6 shown, a flow disturbance component 14 is installed on one outer wall of the top of the housing 11 through bolts. The flow disturbance component 14 includes a pump body 27. The model of the pump body 27 is preferably the Iwaki MD series corrosion-resistant diaphragm pump. The pump body 27 is installed at the center of the top of the housing 11 through bolts. A liquid suction pipe 33 is inserted at the feed end of the pump body 27. The pump body 27 can extract the electrolyte through the liquid suction pipe 33, and the liquid suction pipe 33 extends into the transparent cover body 1. Filter boxes one 25 and two 26 are respectively installed on both outer walls of the pump body 27 through bolts, and the filter boxes one 25 and two 26 are communicated with the discharge end of the pump body 27 through pipes. Installation grooves 28 are provided on one outer wall of the top of the filter boxes one 25 and two 26, and a cover plate 31 is installed inside the installation groove 28 through bolts. A filter element 32 is installed on one outer wall of the bottom of the cover plate 31 through bolts. The filter element 32 is preferably made of PES (polyethersulfone) material. Connection pipes 29 are respectively inserted on one outer wall of the filter boxes one 25 and two 26, and a plurality of return pipes 30 are respectively inserted on both outer walls of the bottom of the connection pipes 29. When the device operates, the pump body 27 will extract the electrolyte in the transparent cover body 1 through the liquid suction pipe 33 and transport it to the filter boxes one 25 and two 26. The filter element 32 will intercept the biomass residues, and the purified electrolyte will be re-injected into the gap between the photocatalytic plate and the conversion plate through the return pipes 30 to form a closed-loop cycle. And during this process, the jet impact of the return pipes 30 will enhance the turbulent effect in the pores, greatly improving the conversion rate of the biomass raw materials. The two groups of return pipes 30 are respectively located between the photocatalytic plate one 15 and the conversion plate one 16, and between the photocatalytic plate two 18 and the conversion plate two 19.

[0034] Working principle: When photocatalytic hydrogen production occurs, the strip board 5 outside the transparent cover 1 emits multi-band light of 400 - 700 nm, which excites the honeycomb photocatalytic nanosheets on the photocatalytic plate one 15 and the photocatalytic plate two 18; photo-generated electrons jump from the valence band to the conduction band and contact the electrolyte water or biomass-containing wastewater in the channel 21 of the substrate 20 to decompose water to produce hydrogen. During the subsequent conversion of biomass electrons, the honeycomb catalysts on the conversion plate one 16 and the conversion plate two 19 adsorb the organic matter in the wastewater and release electrons through enzymatic catalytic reactions. The biomass electrons are transmitted to the proton exchange plate 17 through the through holes 23 in the embedding groove 22 and participate in the hydrogen production reaction synergistically with the photo-generated electrons; as the reaction proceeds, mass transfer and proton exchange occur, and a multi-stage permeation network is formed by the channel 21 and the through holes 23 of the substrate 20. After the electrolyte is injected into the housing 11 through the grouting pipe 12, it quickly diffuses to each layer board along the channel 21. With the synergistic effect of the micron-level channel 21 and the nano-level through holes 23, the electrolyte permeation rate will be greatly improved; at the same time, the filling block 24 of the proton exchange plate 17 selectively conducts hydrogen ions and prevents biomass residues from entering the photocatalytic area. The hydrogen ions generated by photocatalysis are transferred to the interfaces of the conversion plate one 16 and the conversion plate two 19 through the membrane and combine with the biomass electrons to generate hydrogen; the hydrogen is discharged from the hydrogen outlet pipe 6, and other gases are discharged from the exhaust pipe 8; when the device is operating, the pump body 27 pumps the electrolyte in the transparent cover 1 through the liquid suction pipe 33 and transports it to the filter box one 25 and the filter box two 26. The filter element 32 intercepts the biomass residues, and the purified electrolyte is re-injected into the gap between the photocatalytic plate and the conversion plate through the return pipe 30 to form a closed-loop cycle.

[0035] Only some exemplary embodiments of the present invention have been described above by way of illustration. Without doubt, for those of ordinary skill in the art, the described embodiments can be modified in various different ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and description are illustrative in nature and should not be construed as limiting the scope of protection of the claims of the present invention.

Claims

1. A three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device, comprising a transparent cover body (1), characterized in that: The other end of the transparent cover (1) is installed with a bottom cover assembly (2) through bolts. The bottom cover assembly (2) includes a housing (11). On both outer walls of the top of the housing (11), grouting pipes (12) are welded. One end of the grouting pipe (12) is threadedly connected with a pipe cap (13). The bottom cover assembly (2) further includes a first photocatalytic plate (15), a first conversion plate (16), a proton exchange plate (17), a second photocatalytic plate (18) and a second conversion plate (19). The first photocatalytic plate (15), the first conversion plate (16), the proton exchange plate (17), the second photocatalytic plate (18) and the second conversion plate (19) are all welded on the outer wall of one side of the bottom of the housing (11). The first photocatalytic plate (15), the first conversion plate (16), the proton exchange plate (17), the second photocatalytic plate (18) and the second conversion plate (19) are distributed in sequence from front to back. The first photocatalytic plate (15), the first conversion plate (16), the proton exchange plate (17), the second photocatalytic plate (18) and the second conversion plate (19) all include a substrate (20). A cavity (21) is formed on the top of the substrate (20), and the cavity (21) communicates with the housing (11). A plurality of embedding grooves (22) are formed on the outer wall of one side of the substrate (20), and a filling block (24) is embedded in the embedding groove (22). A plurality of through holes (23) are formed on the inner wall of the embedding groove (22), and the through holes (23) communicate with the cavity (21).

2. The three-dimensional porous bifunctional photocatalytic hydrogen production membrane electrode device according to claim 1, wherein, A groove (4) is formed on the outside of the transparent cover (1), and a lamp strip board (5) is wound inside the groove (4).

3. A three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device according to claim 1, characterized in that, One end of the transparent cover (1) is installed with a top cover (3) through bolts. Hydrogen outlet pipes (6) and exhaust pipes (8) are respectively inserted on both outer walls of the top of the top cover (3). Electrode seats (7) are installed on both outer walls of the top of the top cover (3) through bolts.

4. The three-dimensional porous bifunctional photo-biological hydrogen production membrane electrode device according to claim 3, characterized in that Two grid plates (10) are installed inside the transparent cover (1) through bolts, and the grid plates (10) are electrically connected to the electrode seats (7) through wires.

5. A three-dimensional porous bifunctional photocatalytic hydrogen production membrane electrode device according to claim 1, characterized in that An installation groove (9) is formed at one end of the transparent cover (1), and the housing (11) is installed inside the installation groove (9) through bolts.

6. A three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device according to claim 1, characterized in that, The filling blocks (24) on the first photocatalytic plate (15) and the second photocatalytic plate (18) are honeycomb photocatalytic nanosheets. The filling blocks (24) on the first conversion plate (16) and the second conversion plate (19) are honeycomb biomass conversion catalysts. The filling blocks (24) on the proton exchange plate (17) are proton exchange membranes.

7. A three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device according to claim 1, wherein, A flow disturbance assembly (14) is installed on the outer wall of one side of the top of the housing (11) through bolts. The flow disturbance assembly (14) includes a pump body (27). The pump body (27) is installed at the center of the top of the housing (11) through bolts. A liquid suction pipe (33) is inserted at the feed end of the pump body (27), and the liquid suction pipe (33) extends into the transparent cover (1).

8. A three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device according to claim 7, characterized in that, Filter boxes one (25) and two (26) are respectively installed on both outer walls of the pump body (27) through bolts, and the filter boxes one (25) and two (26) are communicated with the discharge end of the pump body (27) through pipelines.

9. A three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device according to claim 8, characterized in that On one side of the outer walls at the top of the first filter box (25) and the second filter box (26), placement grooves (28) are provided, and a cover plate (31) is installed inside the placement grooves (28) through bolts. On one side of the outer wall at the bottom of the cover plate (31), a filter element (32) is installed through bolts.

10. A three-dimensional porous bifunctional photocatalytic biomass hydrogen production membrane electrode device according to claim 8, characterized in that, On one side of the outer walls of the first filter box (25) and the second filter box (26), connecting pipes (29) are inserted. On both sides of the outer walls at the bottom of the connecting pipes (29), a plurality of return pipes (30) are inserted. The two groups of return pipes (30) are respectively located between the first photocatalytic plate (15) and the first conversion plate (16), and between the second photocatalytic plate (18) and the second conversion plate (19).

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