Stepped sample introduction photocatalytic water splitting hydrogen production sample introduction device

Abstract

The invention relates to the technical field of renewable energy source large-scale preparation, in particular to a stepped sample introduction photocatalytic water splitting hydrogen production sample introduction device which comprises a photocatalytic sample introduction device, a sample introduction device hollow interlayer, a port catalyst magnetic suction vessel and an inner cavity. The photocatalyst sample injector is wrapped with a sample injector outer-layer condensation sleeve, a sample injector hollow interlayer is arranged in the photocatalyst sample injector, tempered glass is arranged between the hollow interlayer and an inner cavity, the stepped double-track is a double-track with the side wall transversely opened, and a pressure buffering port is formed in the stepped double-track. According to the photocatalytic hydrogen production sampling system disclosed by the invention, the stepped double tracks are arranged in the photocatalyst sampler, so that the rate of a photocatalyst entering a reactor through the sampler is increased, the loss of the catalyst is reduced, the pressure difference between the inner cavity of the sampler and the catalyst magnetic suction vessel is promoted, and the photocatalyst is uniformly dispersed in the sampling stage; the utilization efficiency of the photocatalyst is improved, the operation cost is saved and the loss of a sample injector is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of renewable energy scale preparation technology, in particular to a stepped sampling device for photocatalytic water decomposition and hydrogen production. BACKGROUND

[0002] Under the background of energy transformation, the future hydrogen energy industry will usher in major development opportunities. Hydrogen energy industry is highly technology-intensive, widely covered, and strongly driven, which is of great significance to reducing greenhouse gas emissions such as carbon dioxide and achieving the goal of carbon peak and carbon neutralization. Existing hydrogen production technologies include water electrolysis, biomass hydrogen production and other routes, among which photocatalytic hydrogen production is hailed as the core technology to solve many problems of future carbon-based energy.

[0003] At present, the sampling technology of natural light photocatalytic hydrogen production mainly exists in two modes of pumping and gravity, but both face the challenges of energy efficiency and stability. In the field of gravity sampling, the light-concentrating fixed film device proposed in the invention patent with publication number CN111453696A optimizes light distribution through a composite parabolic concentrator, but the static light-concentrating design leads to the lack of solar tracking capability, and the light-concentrating ratio limits the space for light intensity improvement. Although the invention patent with publication number CN103861542A realizes automatic solar tracking, it still relies on manual gravity sampling, which has the problems of complicated operation and catalyst loss. The photocatalytic water decomposition and hydrogen production reaction devices disclosed in the above two invention patents are both provided with liquid storage tanks, and the gravity flow mode in the sampling process is introduced into the reactor by external force, which causes a large amount of electric energy loss, increases the operation cost, and easily causes the blocking and aging of the sampling system during the reaction process. In the field of pumping sampling, the invention patent with publication number CN1710284A provides a centrifugal pump self-suction jet flow automatic closing loop system, but still has the problem of low pump efficiency caused by liquid circulation of the self-suction backflow hole. SUMMARY

[0004] The purpose of the present application is to provide a device that does not need to consume a large amount of electric energy, can quickly sample, effectively reduces the sampling loss, and fully disperses the photocatalyst.

[0005] In order to achieve the above object, the present application provides the following technical scheme: a stepped sampling light catalytic water decomposition hydrogen sampling device, comprising a light catalytic sampler, a sampler hollow interlayer, a port catalyst magnetic suction vessel and a light catalytic reactor, an inner cavity is arranged in the light catalytic sampler, the sampler hollow interlayer and the inner cavity are separated by tempered glass, a sampling port is arranged at the bottom of the light catalytic sampler, a sampling valve is arranged at the sampling port, and the sampling port is sealingly connected with the port catalyst magnetic suction vessel, a magnetic rotor is arranged in the port catalyst magnetic suction vessel, and an electromagnetic coil is wound on the outer wall, an outlet port is arranged at the top of the light catalytic sampler, an outlet valve is arranged at the outlet port, and the outlet port is sealingly connected with the sampling port of the light catalytic reactor; an outer layer light condensing sleeve is wrapped outside the light catalytic sampler, an outer wall solar cell is arranged on the inner wall of the outer layer light condensing sleeve, a solar drive tuning device is arranged at the top of the outer layer light condensing sleeve, and the solar drive tuning device is electrically connected with the outer wall solar cell, the sampling valve, the outlet valve and the magnetic rotor driving device respectively; a stepped double track is arranged in the inner cavity, the stepped double track is a double track structure with a horizontal side wall, the top of the stepped double track is connected with the outlet port, the bottom of the stepped double track is connected with the sampling port, a pressure relief port is arranged in the stepped double track, pressure relief glass shafts are arranged on both sides of the stepped double track, the axis of the pressure relief glass shaft is perpendicular to the center of the inner cavity, and the pressure relief glass shaft is fixedly connected with the pressure relief port.

[0006] Preferably, the light transmittance of the tempered glass is ≥92%, and the thickness is 5-8mm.

[0007] Preferably, the outer layer light condensing sleeve is made of polycarbonate material, the thickness is 8-10cm, and the light transmittance is ≥88%.

[0008] Preferably, the outer wall solar cell is made of monocrystalline silicon material, the conversion efficiency is ≥23%, the total area is 0.5-0.8m 2 .

[0009] Preferably, the volume of the port catalyst magnetic suction vessel is 500-1000mL, the connection between the port catalyst magnetic suction vessel and the sampling port is sealed by a nitrile rubber sealing ring, and a filter screen with a pore size of 5-10μm is arranged at the connection.

[0010] Preferably, the stepped double track is made of quartz glass material, has 3-5 steps, the height difference between adjacent steps is 5-8cm, and the track width is 2-3cm.

[0011] Preferably, a pressure sensor is arranged in the pressure relief port, the measurement range of the pressure sensor is 0-2MPa, and the accuracy is ±0.01MPa.

[0012] Preferably, the solar drive start-up device is built-in with a backup lithium battery, the specification of the backup lithium battery is 12V / 10Ah, and the solar drive start-up device is integrated with an MPPT maximum power tracking module.

[0013] Compared with the prior art, the present application has the following advantages:

[0014] 1. The stepped sampling photocatalytic water decomposition hydrogen production sampling device is provided with a stepped double track in the photocatalyst sampler, so as to increase the rate of photocatalyst passing through the sampler into the reactor, reduce the catalyst loss, and convert the absorbed solar energy into heat energy in the sampling process of the outer light focusing sleeve of the photocatalyst sampler, so as to cause a pressure difference between the inner cavity of the sampler and the catalyst magnetic suction vessel, uniformly disperse the photocatalyst in the sampling stage, improve the utilization efficiency of the photocatalyst, improve the hydrogen production efficiency, simultaneously, without the need of adding a sampling pump, save the operation cost, reduce the loss of the sampler, and have strong adaptability to weather condition changes, simple equipment operation, and low cost.

[0015] 2. The stepped sampling photocatalytic water decomposition hydrogen production sampling device is provided with a stepped sampling system in the photocatalytic reactor, so as to effectively avoid the loss of photocatalyst caused by pump suction sampling or direct injection into the reactor, the impact resistance of the photocatalyst is enhanced by the stepped double track, the stepped double track wall reduces the loss of the photocatalyst, and the photocatalytic water decomposition hydrogen production performance is improved. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiment description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0017] Fig. 1 It is a schematic diagram of the overall structure of the sampling device of the present application.

[0018] Fig. 2 It is a schematic diagram of the internal structure of the photocatalytic sampler of the present application.

[0019] In the figure: 1, photocatalytic sampler; 2, hollow spacer layer in the sampler; 3, port catalyst magnetic suction vessel; 4, outer light focusing sleeve; 5, solar cell; 6, sampling port; 7, stepped double track; 8, solar drive start-up device; 9, sampling valve; 10, sampling outlet; 11, inner cavity; 12, photocatalytic reactor; 13, sampling outlet valve; 14, tempered glass; 16, pressure relief glass shaft; 17, pressure relief port. DETAILED DESCRIPTION

[0020] With reference to the drawings of the embodiments of the present application, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of the present application.

[0021] In the present application, unless specifically defined and limited otherwise, the terms "mounting", "connection", "connecting", "fixing" and the like should be interpreted broadly, for example, can be fixed connection, can also be detachable connection, or integrated; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be the internal communication of two elements or the interaction relationship between two elements. For a person of ordinary skill in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0022] Please refer to Figs. 1-2 The present application provides a technical solution: a stepped sampling device for photocatalytic decomposition of water to produce hydrogen, a photocatalytic sampler 1 is the main body of the device, which is divided into a sampler hollow layer 2 and an inner cavity 11 by a tempered glass 14; the sampling port 6 at the bottom of the photocatalytic sampler 1 is sealingly connected with the port catalyst magnetic attraction vessel 3, the sampling valve 9 is installed in the middle of the sampling port 6, which can control the on-off of the sampling passage; the sampling port 10 at the top of the photocatalytic sampler 1 is sealingly connected with the sampling port of the photocatalytic reactor 12, the sampling valve 13 is installed in the middle of the sampling port 10, which is used to regulate the flow of photocatalyst suspension into the reactor.

[0023] The photocatalytic sampler 1 is wrapped with an outer light concentrating sleeve 4, the outer wall of the light concentrating sleeve 4 is paved with an outer wall solar cell 5, which can efficiently absorb solar energy; a solar-driven tuning device 8 is installed at the top of the light concentrating sleeve 4, which is electrically connected with the outer wall solar cell 5, the sampling valve 9, the sampling valve 13 and the magnetic rotor driving device in the port catalyst magnetic attraction vessel 3, which can store and distribute the electrical energy converted by the solar cell to each electrical component, and can optimize the light energy utilization efficiency through the integrated MPPT maximum power tracking module, and the built-in 12V / 10Ah backup lithium battery can ensure the stable operation of the device when the light is insufficient.

[0024] The stepped double track 7 is arranged in the inner cavity 11, which is a double track structure with the side wall horizontally opened, the top part is communicated with the sample outlet 10, the bottom part is communicated with the sample inlet 6, the buffer glass shaft 16 is arranged on both sides of the track, the axis of the buffer glass shaft 16 is perpendicular to the center of the inner cavity 11 and is fixedly connected with the buffer port 17 in the track, the pressure sensor in the buffer port 17 can monitor the pressure in the track in real time, the measurement range of the pressure sensor is 0-2 MPa, and the accuracy is ±0.01 MPa; the magnetic rotor is arranged in the port catalyst magnetic suction vessel 3, the outer wall is wound with an electromagnetic coil, the magnetic rotor can be used for stirring to prevent the photocatalyst from agglomeration, the magnetic field generated by the electromagnetic coil can be used for assisting the dispersion of the photocatalyst, and a filter screen with a pore size of 5-10 μm is arranged at the connection position of the vessel and the sample inlet 6, so that large-particle impurities in the suspension can be filtered, and the stepped double track 7 is prevented from being blocked.

[0025] Jilin City in Jilin Province of China, east longitude 126.57°, north latitude 43.87°, elevation 219 m, the average annual sunshine duration of the region is about 2400 h, the average light intensity in summer is about 800 W / ㎡, and the average light intensity in winter is about 400 W / ㎡, which is suitable for testing the adaptability of the device under different light conditions, and the specific implementation steps are as follows:

[0026] Check the sealing property of the device: confirm that the nitrile rubber sealing ring is installed at the connection position of the photocatalytic sample injector 1 and the port catalyst magnetic suction vessel 3, there is no leakage at the connection position of the sample outlet 10 and the photocatalytic reactor 12, and the sample valve 9 and the sample valve 13 are in the closed state.

[0027] Prepare the photocatalyst suspension: select TiO2 as the photocatalyst, the particle size of the photocatalyst is 20-50 nm, the photocatalytic activity is high, and the stability is strong, the suspension is prepared according to the mass ratio of 1:150 of the photocatalyst and water, the suspension is injected into the port catalyst magnetic suction vessel 3, the liquid level is controlled to be 75% of the volume of the vessel, and the suspension is prevented from overflowing or the liquid level from being too low to cause interruption of sampling.

[0028] Start the solar-driven timing device 8, set the trigger threshold of the pressure sensor to 1.4 MPa, the pressure difference can ensure the sampling rate and avoid damage caused by excessive pressure in the track, the rotating speed of the magnetic rotor is set to 80 r / min, and the hydraulic residence time of the photocatalyst suspension in the stepped double track 7 is set to 4 h.

[0029] Example 1

[0030] Under the condition of about 800W / ㎡ light intensity in summer sunny day, the outer light focusing cover 4 absorbs solar energy, part of which is converted into electric energy by the outer wall solar cell 5, and is distributed to the magnetic rotor driving device and the valve control module after being driven by the solar driven governor 8; the other part of the light energy is converted into heat energy by the outer light focusing cover 4, and the heat energy is transmitted to the sample injector hollow partition layer 2 through the tempered glass 14, and then diffused to the inner cavity 11 through the hollow partition layer, so that the pressure of the inner cavity 11 gradually increases, and the heat energy conversion efficiency in this process is 85%. When the pressure sensor in the slow pressure port 17 detects that the pressure difference between the inner cavity 11 and the port catalyst magnetic attraction vessel 3 reaches 1.4 MPa, the solar driven governor 8 automatically sends a signal to open the sampling valve 9, and the sampling process is started.

[0031] Under the synergistic effect of 1.4 MPa pressure difference and the magnetic field of the electromagnetic coil on the outer wall of the port catalyst magnetic attraction vessel 3, the photocatalyst suspension is sucked into the ladder double track 7 through the filter screen, and the flow rate is stabilized at 0.2 mL / s through the flow monitoring module of the solar driven governor 8, so as to avoid the aggregation of the catalyst caused by too fast rate or the influence of reaction continuity caused by too slow rate.

[0032] The suspension flows along the 3-stage ladder of the ladder double track 7, and the slow pressure glass shaft 16 cooperates with the slow pressure port 17 to control the pressure fluctuation in the track within ±0.05 MPa; at the same time, the magnetic field generated by the electromagnetic coil promotes the photocatalyst to flip 9 times on the inner wall of the track, and the stirring action of the magnetic rotor effectively breaks the catalyst aggregation, and through sampling detection, the mass of the photocatalyst adhered to the inner wall of the ladder double track 7 is only 0.06% of the total catalyst mass, which is much lower than the catalyst loss rate of the existing gravity sampling device and pump suction sampling device.

[0033] When the hydraulic residence time of the photocatalyst suspension in the ladder double track 7 reaches 4h, the solar driven governor 8 receives the stable pressure signal fed back by the pressure sensor, and automatically opens the sample outlet valve 13, so that the suspension uniformly enters the photocatalytic reactor 12 through the sample outlet 10, at this time, through the hydrogen detection module of the reactor, the hydrogen generation rate is about 180 μmol / (g·h), which is increased by 50% compared with the device of CN111453696A, and is increased by 28.6% compared with the device of CN1710284A. When the liquid level in the port catalyst magnetic attraction vessel 3 is reduced to 20% of the volume, the solar driven governor 8 sends a low liquid level alarm to remind the operator to supplement the suspension; if it is cloudy, the light intensity is about 300W / ㎡, the power generation of the outer wall solar cell 5 is insufficient, and the governor automatically switches to the standby lithium battery power supply, so that the sampling rate can still be stabilized at 0.18-0.2 mL / s, which proves that the device has strong adaptability to weather changes.

[0034] Example 2

[0035] In winter in Jilin City, the light intensity is about 400 W / ㎡, and the performance of the device under low light conditions is verified by supplementary testing. The specific adjustments and results are as follows:

[0036] Due to the decrease in winter light intensity, the thermal energy conversion efficiency of the outer light collection cover 4 is reduced to 80%. To ensure that the pressure difference between the inner cavity 11 and the port catalyst magnetic attraction vessel 3 still reaches 1.4 MPa, the solar-driven regulator 8 is extended to accumulate heat energy for a longer time, and the magnetic rotor speed is reduced to 70 r / min to reduce power consumption.

[0037] The running results are as follows: the sampling rate is stable at 0.19 mL / s, the catalyst adhesion rate of the stepped double-track 7 inner wall is 0.07%, and the hydrogen generation rate of the photocatalytic reactor 12 is about 150 μmol / (g·h), which is about 90 μmol / (g·h) higher than that of the device of CN103861542A under the same conditions, an increase of 66.7%. The standby lithium battery can support the device to run continuously for 4 hours under no light conditions, meeting the sampling demand under intermittent light conditions.

[0038] Through the above examples, the device has the following effects:

[0039] Low energy consumption: No additional sampling pump is needed, and the device relies entirely on solar power. The power consumption during operation is only 15%-20% of that of the existing pump sampling device. According to the industrial electricity price of 1 yuan per degree and the average daily operation of 8 hours, the annual operation cost can be reduced by about 3000 yuan.

[0040] Low catalyst consumption: The stepped double-track 7 and the magnetic attraction dispersion system work together to control the catalyst adhesion rate to 0.06%-0.07%, which is more than 80% lower than that of the existing technology. According to the TiO2 catalyst consumption of 80 yuan / kg and the daily consumption of 0.5 kg, the catalyst replacement cost can be reduced by about 2000 yuan per year.

[0041] Strong adaptability: Within the range of 300-800 W / ㎡ of light intensity, the sampling rate fluctuates only ±5%, the hydrogen generation rate is stable, and the standby lithium battery can cope with short-term no-light conditions, making it suitable for different regions, different seasons, and photocatalytic hydrogen production scene applications.

[0042] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0043] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A stepped sample injection photocatalytic water decomposition hydrogen production sample injection device, comprising a photocatalytic sample injector (1), a sample injector hollow partition layer (2), a port catalyst magnetic attraction vessel (3) and a photocatalytic reactor (12), characterized in that: The photocatalytic sample injector (1) is internally provided with an inner cavity (11), the hollow interlayer (2) of the sample injector is separated from the inner cavity (11) by the tempered glass (14), the bottom of the photocatalytic sample injector (1) is provided with a sample inlet (6), the sample inlet (6) is installed with a sample valve (9), and the sample inlet (6) is sealingly connected with the port catalyst magnetic suction vessel (3), the inner part of the port catalyst magnetic suction vessel (3) is provided with a magnetic rotor, and the outer wall is wound with an electromagnetic coil, the top of the photocatalytic sample injector (1) is provided with a sample outlet (10), the sample outlet (10) is installed with a sample valve (13), and the sample outlet (10) is sealingly connected with the sample inlet of the photocatalytic reactor (12); the outer part of the photocatalytic sample injector (1) is wrapped with an outer light focusing sleeve (4), the inner wall of the outer light focusing sleeve (4) is provided with an outer wall solar cell (5), the top of the outer light focusing sleeve (4) is installed with a solar-driven frequency converter (8), and the solar-driven frequency converter (8) is electrically connected with the outer wall solar cell (5), the sample valve (9), the sample valve (13) and the magnetic rotor driving device respectively; the inner cavity (11) is provided with a stepped double track (7), the stepped double track (7) is a double track structure with a horizontally opened side wall, the top of the stepped double track (7) is connected with the sample outlet (10), the bottom of the stepped double track (7) is connected with the sample inlet (6), the inner part of the stepped double track (7) is provided with a buffer port (17), the both sides of the stepped double track (7) are provided with a buffer glass shaft (16), the axis of the buffer glass shaft (16) is perpendicular to the center of the inner cavity (11), and the buffer glass shaft (16) is fixedly connected with the buffer port (17).

2. The stepped sample introduction photocatalytic water-splitting hydrogen evolution sample introduction device of claim 1, wherein: The light transmittance of the tempered glass (14) is greater than or equal to 92%, and the thickness is 5-8 mm.

3. The stepped sample introduction photocatalytic water-splitting hydrogen evolution sample introduction device of claim 1, wherein: The outer light focusing sleeve (4) is made of polycarbonate material, the thickness is 8-10 cm, and the light transmittance is greater than or equal to 88%.

4. The stepped sample introduction photocatalytic water-splitting hydrogen evolution sample introduction device of claim 1, wherein: The outer wall solar cell piece (5) is made of monocrystalline silicon material, the conversion efficiency is greater than or equal to 23%, and the total area is 0.5-0.8m 2 .

5. The stepped sample introduction photocatalytic water-splitting hydrogen evolution sample introduction device of claim 1, wherein: The volume of the port catalyst magnetic suction vessel (3) is 500-1000 mL, the connection part between the port catalyst magnetic suction vessel (3) and the sample inlet (6) is sealed by a nitrile rubber sealing ring, and the connection part is provided with a filter screen with a pore size of 5-10 μm.

6. The stepped sample introduction photocatalytic water-splitting hydrogen evolution sample introduction device of claim 1, wherein: The stepped double track (7) is made of quartz glass material, and is provided with 3-5 steps, the height difference between adjacent steps is 5-8 cm, and the track width is 2-3 cm.

7. The stepped sample introduction photocatalytic water-splitting hydrogen evolution sample introduction device of claim 1, wherein: The buffer port (17) is internally provided with a pressure sensor, the measurement range of the pressure sensor is 0-2 MPa, and the accuracy is ±0.01 MPa.

8. The stepped sample introduction photocatalytic water-splitting hydrogen evolution sample introduction device of claim 1, wherein: The solar-driven frequency converter (8) is internally provided with a backup lithium battery, the specification of the backup lithium battery is 12V / 10Ah, and the solar-driven frequency converter (8) is integrated with an MPPT maximum power tracking module.

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