Rotational flow oscillation coupling ultrasonic piezoelectric hydrogen production device and method

Abstract

The invention discloses a rotational flow oscillation coupling ultrasonic piezoelectric hydrogen production device and method, a rotational flow ultrasonic coupling reactor is adopted to carry out piezoelectric catalytic hydrogen production, a solid-liquid mixed system dispersed with a piezoelectric catalyst and a cocatalyst is introduced into the rotational flow ultrasonic coupling reactor along the tangential direction at a high speed, and the piezoelectric catalytic hydrogen production is carried out through rotational flow coupling ultrasound; according to the rotational flow coupling ultrasonic piezoelectric hydrogen production method, rotational flow coupling ultrasonic provides driving force, mass transfer is enhanced, and rotational flow degassing is performed, so that the ultrasonic hydrogen production efficiency is remarkably enhanced; the ultrasonic vibration rod serves as a center fixing rod in the rotational flow ultrasonic coupling reactor, a flow field is stabilized in the piezoelectric hydrogen production reaction process, and energy consumption is reduced; and through the combined action of the two, the effect of '1 + 1 > 2' is realized.

Description

Technical Field

[0001] The present invention belongs to the technical fields of wastewater treatment and piezoelectric hydrogen production, and specifically relates to a swirl oscillation coupled ultrasonic piezoelectric hydrogen production device and method. Background Art

[0002] In the context of the carbon emission reduction challenge, hydrogen, as a green, clean, and renewable high-energy density energy source, is of great significance in the search for sustainable development and clean energy solutions. As a secondary energy source, hydrogen can be obtained from water splitting through catalytic redox reactions, which is in line with the general trend of environmental friendliness. Photocatalysis and electrocatalysis, as two mainstream catalytic methods, are widely used in the hydrogen evolution reaction of water splitting. However, photocatalytic hydrogen production depends on light sources with specific wavelengths, and its hydrogen production capacity is limited by the light absorption range and the electron-hole recombination rate. Electrocatalysis has high energy consumption, and most of the catalytic materials involved are precious metals, resulting in high costs. Piezoelectric catalytic hydrogen production utilizes the inexhaustible mechanical energy in nature to stimulate piezoelectric catalytic materials to deform and generate charge transfer, thereby forming a potential difference on the surface of the catalyst and further generating a built-in electric field to drive water decomposition to produce hydrogen.

[0003] Piezoelectric catalytic hydrogen production, with its unique advantage of utilizing mechanical energy, not only conforms to the technical direction of clean energy development but is also an innovative solution to address energy crises and environmental challenges. However, its research and application are still in their infancy. Currently, piezoelectric materials are mainly excited through single methods such as ultrasound, mechanical stirring, and grinding. In laboratories, ultrasound is usually used to excite piezoelectricity. The mechanical vibration of ultrasonic waves provides periodic mechanical force for piezoelectric materials to generate a built-in electric field, thereby driving the decomposition of water molecules to produce hydrogen. However, the single ultrasonic excitation method for piezoelectric hydrogen production still has certain limitations in terms of energy utilization conversion efficiency and mass transfer rate. For example, the phenomenon of bubble shielding during the hydrogen production reaction will reduce the hydrogen production efficiency, and high-frequency ultrasonic oscillations require continuous high-energy input, which is also difficult to meet the actual requirements in terms of equipment stability and adaptability to complex working conditions. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides a swirl oscillation coupled ultrasonic piezoelectric hydrogen production device and method to solve the problems of high energy consumption and low efficiency of ultrasonic excitation of the piezoelectric effect.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] In the first aspect of the present invention, there is provided a swirl oscillation coupled ultrasonic piezoelectric hydrogen production device, comprising

[0007] The swirling ultrasonic coupling reactor includes a first part and a second part located below the first part and communicating with the first part. The first part is a cylindrical section, and three tangential inlets are circumferentially and evenly distributed near the top of its side wall, and an overflow port is provided at the top; tangential inlet pipelines are provided at the three tangential inlets, and an overflow pipeline is provided at the overflow port; the second part is a conical section, and a bottom flow port is provided at its bottom, and a bottom flow pipeline is provided at the bottom flow port;

[0008] The ultrasonic generating device includes an ultrasonic vibrating rod and an ultrasonic generator. The ultrasonic generator and the ultrasonic vibrating rod are electrically connected, and the ultrasonic vibrating rod is fixed inside the swirling ultrasonic coupling reactor;

[0009] The liquid storage tank is provided with a liquid outlet pipeline at its lower part, a first reflux port and a second reflux port at its upper part; the liquid outlet pipeline is connected to the tangential inlet pipeline; the overflow pipeline is connected to the first reflux port, and the bottom flow pipeline is connected to the second reflux port;

[0010] A centrifugal pump is arranged on the liquid outlet pipeline and is used to pump the liquid in the liquid storage tank into the swirling ultrasonic coupling reactor.

[0011] Further, the tangential inlet is rectangular.

[0012] The tangential inlet of the swirling ultrasonic coupling reactor is set to be rectangular. Compared with the circular inlet, the rectangular inlet can better guide the fluid into the interior of the swirling ultrasonic coupling reactor, reduce the eddy current and disturbance of the fluid at the tangential inlet, and can better stabilize the entire swirling flow field; at the same time, the long side of the rectangular inlet is closely attached to the column section wall of the swirling ultrasonic coupling reactor, which can effectively eliminate the dead zone of the feed short circuit and further improve the separation effect; and the design of the rectangular inlet makes the swirling ultrasonic coupling reactor have stronger adaptability when dealing with fluids of different flow rates and velocities. By adjusting the inlet size, it can flexibly adapt to different process requirements and improve the versatility and flexibility of the equipment.

[0013] Further, the ultrasonic vibrating rod is fixed at the central axis of the swirling ultrasonic coupling reactor through three identical brackets.

[0014] The ultrasonic vibrating rod is fixed at the central axis of the swirling ultrasonic coupling reactor and acts as a central fixed rod, which can effectively reduce the volume of the air column, thereby reducing energy consumption; the presence of the central fixed rod can change the flow field distribution inside the swirling ultrasonic coupling reactor, reduce the turbulence intensity in the central area, make the flow field distribution of the fluid inside the swirling ultrasonic coupling reactor more uniform, and avoid the phenomenon of local over-flow or dead zone, further improving the stability of the equipment.

[0015] Furthermore, the lengths of the three tangential inlets are 50 mm to 100 mm, the widths are 100 mm to 200 mm, and they are all inclined downward at an angle of 0° to 60°. The three tangential inlets are symmetrically and uniformly distributed at 120° on the side wall of the swirl ultrasonic coupling reactor.

[0016] This design can not only ensure a more uniform flow field distribution inside the swirl ultrasonic coupling reactor and improve the stability of the flow field, but also, with the inlets inclined downward at a certain angle (0° to 60°), generate a stronger shear force when the fluid enters the swirl ultrasonic coupling reactor, optimizing the swirl piezoelectric effect.

[0017] Furthermore, the lengths of the three tangential inlets are 50 mm, the widths are 100 mm, and they are all inclined downward at an angle of 45°. The three tangential inlets are symmetrically and uniformly distributed at 120° on the side wall of the swirl ultrasonic coupling reactor.

[0018] This design can ensure the stability of the flow field and provide the maximum input momentum. With all three inlets inclined downward tangentially at 45°, this structure helps to guide the fluid to enter tangentially along the inner wall of the swirl ultrasonic coupling reactor, quickly forming a strong three-dimensional rotating flow field.

[0019] Furthermore, the diameter of the first cylindrical section is DN250 to DN500, and the length is 200 mm to 400 mm; the cone angle of the second conical section is 6° to 10°, the diameter of the overflow port is 100 mm to 150 mm, and the diameter of the underflow port is 100 mm to 150 mm; the diameter of the ultrasonic vibration rod is 50 to 80 mm, the length is 200 mm - 400 mm, and the material is SUS304.

[0020] Furthermore, the diameter of the first cylindrical section is DN250, and the length is 370 mm; the cone angle of the second conical section is 7°, the diameter of the overflow port is 100 mm, and the diameter of the underflow port is 100 mm; the diameter of the ultrasonic vibration rod is 52 mm, and the length is 300 mm.

[0021] Furthermore, the ultrasonic power of the ultrasonic vibration rod is 120 to 1800 w, and the ultrasonic frequency is 20 KHz to 40 KHz.

[0022] The second aspect of the present invention is to provide a method for producing hydrogen by swirl oscillation coupled ultrasonic piezoelectricity. Using the above-mentioned swirl oscillation coupled ultrasonic piezoelectric hydrogen production device, it includes the following steps:

[0023] S1. Uniformly disperse piezoelectric catalyst particles and co-catalyst particles into water to obtain a first solution, and place it in a liquid storage tank; turn on the ultrasonic generating device;

[0024] S2. The first solution in the liquid storage tank is introduced into the swirl ultrasonic coupling reactor along the three tangential inlets at a first speed by a centrifugal pump respectively, forming a strong three-dimensional rotating flow field in the swirl ultrasonic coupling reactor. Through the combined action of swirl oscillation and ultrasonic oscillation, the piezoelectric effect of the piezoelectric catalyst is excited to generate hydrogen gas.

[0025] S3. Hydrogen gas, a small part of water, a small amount of catalyst, and promoter particles are discharged from the overflow port and enter the liquid storage tank, and the hydrogen gas is temporarily stored above the liquid level of the liquid storage tank; the first solution after the swirl ends is discharged from the underflow port and returned to the liquid storage tank.

[0026] S4. Repeat steps S2 to S3 until the entire reaction ends.

[0027] Further, the first speed is 1 m / s to 8 m / s.

[0028] Control the tangential flow rate of the first solution entering the swirl ultrasonic coupling reactor to be 1 m / s to 8 m / s; it can not only ensure the coupling piezoelectric effect of swirl oscillation and ultrasonic oscillation, but also will not cause over-excitation to the piezoelectric catalyst particles, resulting in mechanical fatigue and damaging the integrity of its structure and reducing the catalytic activity.

[0029] Compared with the prior art, the present invention has at least the following beneficial effects:

[0030] 1. The swirl oscillation coupling ultrasonic piezoelectric hydrogen production device and method provided by the present invention utilize the combined action of swirl oscillation and ultrasonic oscillation in the swirl ultrasonic coupling reactor to excite the piezoelectric effect of the piezoelectric catalyst particles. The swirl oscillation coupling ultrasonic oscillation provides a periodic mechanical driving force for the piezoelectric catalyst particles. During the piezoelectric catalytic hydrogen production process, it can not only enhance the mass transfer ability, solve the energy consumption (reduce the energy consumption required in the ultrasonic-excited piezoelectric hydrogen production process) and mass transfer bottleneck in the single ultrasonic-excited piezoelectric hydrogen production process, but also overcome the bubble shielding phenomenon, realize the rapid detachment of hydrogen gas, and improve the hydrogen production efficiency.

[0031] 2. The swirl oscillation coupling ultrasonic piezoelectric hydrogen production device and method provided by the present invention mainly utilize the strong three-dimensional rotating flow field inside the swirl ultrasonic coupling reactor, and significantly enhance the efficiency of ultrasonic hydrogen production through three aspects: providing driving force by swirl coupling ultrasonic, strengthening mass transfer, and swirl degassing; in addition, the ultrasonic vibration rod acts as a central fixed rod in the swirl ultrasonic coupling reactor, stabilizing the flow field and reducing energy consumption during the piezoelectric hydrogen production reaction; overall, the swirl oscillation coupling ultrasonic oscillation can achieve high-efficiency hydrogen production under the conditions of low flow rate (swirl flow rate: the flow rate of the first solution entering the swirl ultrasonic coupling reactor) and low frequency (ultrasonic oscillation + swirl oscillation).

[0032] 3. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device and method provided by the present invention. The three-dimensional rotating flow field in the swirl ultrasonic coupling reactor enhances the mass transfer efficiency in the ultrasonic-excited piezoelectric hydrogen production process, strengthens the hydrogen production process by water decomposition, and at the same time can achieve efficient gas-liquid separation under the action of the pressure gradient. This process requires no additional energy consumption and has high efficiency and stability. Moreover, during the reaction process, the ultrasonic vibration rod can, on the one hand, excite the piezoelectric effect through periodic ultrasonic waves, and on the other hand, serve as the central column of the swirl ultrasonic coupling reactor, playing a role in stabilizing the flow field and optimizing the swirl structure.

[0033] 4. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device and method provided by the present invention. Compared with separate ultrasonic hydrogen production and separate piezoelectric hydrogen production, the swirl coupling ultrasonic significantly enhances the efficiency of ultrasonic hydrogen production in three aspects: providing driving force, strengthening mass transfer, and swirl degassing. The ultrasonic vibration rod acts as a central solid rod in the swirl ultrasonic coupling reactor, stabilizing the flow field and reducing energy consumption during the piezoelectric hydrogen production reaction. The two work together to achieve the effect of "1 + 1 > 2". Brief Description of the Drawings

[0034] Figure 1 is a schematic process flow diagram of swirl oscillation coupled ultrasonic piezoelectric hydrogen production of the present invention.

[0035] Figure 2 is a schematic diagram of swirl oscillation coupled ultrasonic piezoelectric hydrogen production in the swirl ultrasonic coupling reactor of the present invention.

[0036] Figure 3 is a schematic structural diagram of the ultrasonic generating device.

[0037] In the figure: 10 - swirl ultrasonic coupling reactor; 11 - first part; 12 - tangential inlet; 121 - tangential inlet pipeline; 13 - overflow port; 131 - overflow pipeline; 14 - second part; 15 - underflow port; 151 - underflow pipeline;

[0038] 20 - ultrasonic generating device; 21 - ultrasonic generator; 22 - ultrasonic vibration rod; 221 - bracket;

[0039] 30 - liquid storage tank; 31 - liquid outlet pipeline; 32 - first reflux port; 33 - second reflux port; 34 - hydrogen gas outlet; 341 - hydrogen gas output pipeline;

[0040] 40 - centrifugal pump;

[0041] F1 - catalyst particles; P1 - hydrogen gas. Detailed Embodiments

[0042] The following further elaborates the present invention in combination with specific embodiments. However, it should be understood that these embodiments are only used to illustrate the present invention and do not constitute a limitation to the scope of the present invention.

[0043] In the following examples, the test methods without specific conditions are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, all percentages and parts are by weight.

[0044] Example 1: Swirl-coupled ultrasonic piezoelectric hydrogen production device and method

[0045] 1.1 Swirl oscillation-coupled ultrasonic piezoelectric hydrogen production device

[0046] See Figures 1 to 3 , this example provides a swirl oscillation-coupled ultrasonic piezoelectric hydrogen production device, including:

[0047] A swirl ultrasonic coupling reactor 10, including a first part 11 and a second part 14 located below the first part 11 and communicating with the first part 11. The first part 11 is a cylindrical section, and three tangential inlets 12 are circumferentially and evenly distributed near the top of its side wall. An overflow port 13 is provided at the top; Tangential inlet pipelines 121 are provided at the three tangential inlets 12, and an overflow pipeline 131 is provided at the overflow port 13; The second part 14 is a conical section, and a bottom flow port 15 is provided at its bottom. A bottom flow pipeline 151 is provided at the bottom flow port 15;

[0048] See Figure 3 , an ultrasonic generating device 20, including an ultrasonic vibrating rod 22 and an ultrasonic generator 21. The ultrasonic generator 21 and the ultrasonic vibrating rod 22 are electrically connected, and the ultrasonic vibrating rod 22 is fixed inside the swirl ultrasonic coupling reactor 10;

[0049] Continue to see Figure 1 , a liquid storage tank 30, with a liquid outlet pipeline 31 provided near the bottom of its side wall, a first reflux port 32, a second reflux port 33 and a hydrogen outlet 34 provided at the top; A hydrogen output pipeline 341 is provided at the hydrogen outlet 34; The liquid outlet pipeline 31 is connected to the tangential inlet pipeline 121; The overflow pipeline 131 is connected to the first reflux port 32, and the bottom flow pipeline 151 is connected to the second reflux port 33;

[0050] A centrifugal pump 40 is arranged on the liquid outlet pipeline 31 for pumping the liquid in the liquid storage tank 30 into the swirl ultrasonic coupling reactor 10.

[0051] In a preferred embodiment of the present invention, the three tangential inlets 12 are rectangular; the tangential inlets 12 are arranged to be rectangular. Compared with the circular inlet, the rectangular inlet can better guide the fluid into the internal of the swirl ultrasonic coupling reactor 10, reduce the eddy current and disturbance of the fluid at the tangential inlet 12, and can better stabilize the entire swirl field; at the same time, the long side of the rectangular inlet is closely attached to the column wall of the swirl ultrasonic coupling reactor 10, which can effectively eliminate the dead zone of the feed short circuit and further improve the separation effect; and the design of the rectangular inlet enables the swirl ultrasonic coupling reactor 10 to have stronger adaptability when processing fluids with different flow rates and velocities. By adjusting the inlet size, it can flexibly adapt to different process requirements and improve the versatility and flexibility of the equipment.

[0052] In a preferred embodiment of the present invention, the ultrasonic vibration rod 22 is fixed at the central axis of the swirl ultrasonic coupling reactor 10 through three identical brackets 221. By fixing the ultrasonic vibration rod 22 at the central axis of the swirl ultrasonic coupling reactor 10 to act as a central fixing rod, the volume of the air column can be effectively reduced, thereby reducing energy consumption; the presence of the central fixing rod can change the flow field distribution inside the swirl ultrasonic coupling reactor 10, reduce the turbulence intensity in the central region, make the flow field distribution of the fluid inside the swirl ultrasonic coupling reactor 10 more uniform, and avoid the phenomenon of local over-flow or dead zone, further improving the stability of the equipment.

[0053] In a preferred embodiment of the present invention, the three tangential inlets 12 are 50 mm to 100 mm in length, 100 mm to 200 mm in width, and all of them are inclined downward by 0° to 60°. The three tangential inlets 12 are symmetrically and uniformly distributed at 120° on the side wall of the swirl ultrasonic coupling reactor 10;

[0054] This design can not only ensure that the flow field distribution of the fluid inside the swirl ultrasonic coupling reactor 10 is more uniform and improve the stability of the flow field; the inlet is inclined downward by a certain angle (0° to 60°), which can make the fluid generate a stronger shear force when entering the swirl ultrasonic coupling reactor 10 and optimize the swirl piezoelectric effect.

[0055] In a preferred embodiment of the present invention, the diameter of the cylindrical section of the first part 11 is DN250 to DN500, and the length is 200 mm to 400 mm; the cone angle of the conical section of the second part 14 is 6° to 10°, the diameter of the overflow port 13 is 100 mm to 150 mm, and the diameter of the underflow port 15 is 100 mm to 150 mm; the diameter of the ultrasonic vibration rod 22 is 50 to 80 mm, the length is 200 mm - 400 mm, and the material is SUS304.

[0056] Using the swirl ultrasonic coupling reactor MoS 2For piezoelectric catalytic hydrogen production, the preferred equipment structure parameters are as follows: The swirl ultrasonic coupling reactor has three tangential inlets 12 with a size of 50mm * 100m, and they all incline downward at an angle of 45°. Each tangential inlet 12 is evenly distributed on the side wall of the swirl ultrasonic coupling reactor 10 at an interval of 120°. This design can ensure the stability of the flow field and provide the maximum input momentum. The three inlets all incline downward tangentially at 45°. This structure helps to guide the fluid to enter tangentially along the inner wall of the swirl ultrasonic coupling reactor 10 and quickly form a strong three-dimensional rotating flow field. The diameter of the cylindrical section of the first part 11 of the swirl ultrasonic coupling reactor 10 is DN250, and the length is 370mm. The cone angle of the second part 14, the conical section, is 7°, the diameter of the overflow port 13 is 100mm, and the diameter of the underflow port 15 is 100mm. The diameter of the ultrasonic vibration rod is 52mm, and the length is 300mm.

[0057] During the hydrogen production reaction process, first, turn on the ultrasonic generating device 20. The first solution dispersed with piezoelectric catalyst particles is fed into the interior of the swirl ultrasonic coupling reaction 10 at high speed from three tangential inlets with an inclination angle (inclining downward from 0° to 60°) under the action of a centrifugal pump. During the reaction process, the ultrasonic vibration rod 22 transmits high-frequency vibrations to the piezoelectric catalyst particles in the first solution. The piezoelectric catalyst particles generate an internal electric dipole structure offset under the action of ultrasonic waves, forming an electric field and charge separation, generating a built-in electric field, thereby driving the decomposition of water molecules to produce hydrogen. At the same time, ultrasonic waves can generate cavitation bubbles in water, and 10 can be excited during the bubble rupture process. 8The high energy of pa accelerates the water decomposition to produce hydrogen. Since the first solution is introduced tangentially at a high speed into the vortex ultrasonic coupling reaction zone 10, a strong three-dimensional rotating flow field will be formed in the vortex ultrasonic coupling reactor 10. The piezoelectric catalyst particles located in the three-dimensional rotating flow field will be simultaneously affected by the vortex oscillation, that is, the three-dimensional rotating flow field coupling ultrasonic significantly enhances the efficiency of ultrasonic hydrogen production from three aspects: providing driving force, strengthening mass transfer, and vortex degassing. In terms of providing driving force, the piezoelectric catalyst material particles in the three-dimensional rotating flow field generate vortex oscillation under the action of unbalanced shear stress during self-rotation. This vortex oscillation exists everywhere inside the vortex ultrasonic coupling reaction zone 10 and can couple with ultrasonic oscillation to generate stronger mechanical stress, further enhancing the piezoelectric effect. This vortex oscillation is a kind of coupled centrifugal force. Under the action of this strong coupled centrifugal force, the tiny hydrogen bubbles generated on the surface of the piezoelectric catalyst particles will be quickly stripped, which can avoid the bubble shielding effect and improve the continuity of the reaction. In terms of mass transfer, the strong turbulence (there is strong turbulence inside the three-dimensional rotating flow field) and shear stress inside the vortex ultrasonic coupling reaction zone 10 can enhance the relative flow between the surface of the piezoelectric catalyst particles and the liquid phase interface, increase the concentration gradient of the reactants on the surface of the piezoelectric catalyst particles, and then enhance the progress of the water decomposition reaction and the hydrogen production capacity. The liquid with a higher density inside the vortex ultrasonic coupling reaction zone 10 is pushed to the outer wall, while the generated hydrogen with a lower density forms a low-pressure area together with part of the liquid in the center of the vortex ultrasonic coupling reaction zone 10. Under the action of this pressure gradient, the hydrogen gas is released from the liquid and accumulates in the low-pressure area, and is discharged from the overflow port 13 at the top of the vortex ultrasonic coupling reaction zone 10, which can efficiently achieve gas-liquid separation. This vortex degassing method does not require additional energy consumption and has high efficiency and stability.

[0058] The ultrasonic vibrator 22 is fixed at the central position of the cylindrical section of the vortex ultrasonic coupling reaction zone 10. On the one hand, it can realize the function of ultrasonic propagation of periodic sound waves. On the other hand, this ultrasonic vibrator 22 can act as a central fixed rod inside the vortex ultrasonic coupling reaction zone 10, playing the role of stabilizing the flow field, optimizing the vortex, and reducing energy consumption. In particular, this central fixed rod can limit the size and shape of the gas core inside the vortex ultrasonic coupling reaction zone 10, making the low-pressure area inside the vortex ultrasonic coupling reaction zone 10 more stable, which is beneficial to the aggregation and discharge of hydrogen. The central fixed rod can also change the fluid path during the reaction, making the liquid phase and the piezoelectric catalyst particles rotate around the column (central fixed rod), enhancing the residence time of the fluid and the piezoelectric catalyst particles in the vortex ultrasonic coupling reaction zone 10, enhancing the excitation time of the ultrasonic and the flow field on the piezoelectric catalyst particles, strengthening the piezoelectric effect, and improving the hydrogen production capacity.

[0059] The water involved in the above process can be pure water, seawater, petrochemical wastewater, etc., and the piezoelectric catalytic material particles involved are BaTiO 3 、ZnO、MoS 2Piezoelectric materials etc.

[0060] Furthermore, the ultrasonic power of the ultrasonic vibration rod 22 is 120 - 1800 w, and the ultrasonic frequency is 20KHz - 40KHz.

[0061] 1.2 Vortex oscillation coupled ultrasonic piezoelectric hydrogen production method

[0062] The vortex oscillation coupled ultrasonic piezoelectric hydrogen production method of this embodiment uses the vortex oscillation coupled ultrasonic piezoelectric hydrogen production device of 1.1 above, and includes the following steps:

[0063] S1. Uniformly disperse piezoelectric catalyst particles and cocatalyst particles into water to obtain a first solution, and place it in the liquid storage tank 30; turn on the ultrasonic generating device 20;

[0064] S2. Through the centrifugal pump 40, the first solution in the liquid storage tank 30 is respectively introduced into the vortex ultrasonic coupling reactor 10 at a speed of 1m / s - 8m / s along the three tangential inlets 12, forming a strong three-dimensional rotating flow field in the vortex ultrasonic coupling reactor 10. Through the combined action of vortex oscillation and ultrasonic oscillation, the piezoelectric effect of the piezoelectric catalyst is excited to generate hydrogen;

[0065] S3. Hydrogen, a small part of water, a small amount of catalyst, and cocatalyst particles are discharged from the overflow port 13 and enter the liquid storage tank 30. Hydrogen is temporarily stored above the liquid level of the liquid storage tank 30; the first solution after the vortex flow ends is discharged from the underflow port 15 and returned to the liquid storage tank 30;

[0066] S4. Repeat steps S2 - S3 until the entire reaction ends;

[0067] S5. After the reaction ends, hydrogen is discharged from the hydrogen outlet 34 and enters the subsequent treatment process through the hydrogen output pipeline 341.

[0068] Control the tangential flow rate of the first solution entering the vortex ultrasonic coupling reactor to be 1m / s - 8m / s; it can not only ensure the coupled piezoelectric effect of vortex oscillation and ultrasonic oscillation, but also will not cause over-excitation to the piezoelectric catalyst particles, resulting in mechanical fatigue, damaging the integrity of its structure, and reducing the catalytic activity.

[0069] Application Example 1 Vortex oscillation coupled ultrasonic piezoelectric hydrogen production

[0070] This embodiment uses the above-mentioned swirl oscillation coupled ultrasonic piezoelectric hydrogen production device in 1.1, and its dimensions are as follows: the diameter of the cylindrical section of the first part 11 is DN250, and the length is 370 mm; the cone angle of the conical section of the second part 14 is 7°, and the dimensions of the three tangential inlets 12 are 50 mm * 100 m, and they all slope downward at 45°. Each tangential inlet 12 is evenly distributed on the side wall of the swirl ultrasonic coupling reactor 10 at an interval of 120°; the diameter of the overflow port 13 is 60 mm, and the diameter of the underflow port 15 is 60 mm; the swirl coupling ultrasonic piezoelectric hydrogen production of this embodiment includes the following steps:

[0071] S11. 180 g of MoS 2 nanosheet flowers (piezoelectric catalyst particles) and 120 g of iron powder (promoter particles) are evenly dispersed in 100 L of pure water to obtain a first solution, which is placed in the liquid storage tank 30; turn on the ultrasonic generating device 20 (ultrasonic frequency 28 KHz, ultrasonic power 120 w);

[0072] S12. The first solution in the liquid storage tank 30 is respectively introduced into the swirl ultrasonic coupling reactor 10 through the three tangential inlets 12 at a speed of 3.3 m / s by the centrifugal pump 40, and a strong three-dimensional rotating flow field is formed in the swirl ultrasonic coupling reactor 10. Through the combined action of swirl oscillation and ultrasonic oscillation, the piezoelectric effect of the piezoelectric catalyst is excited to generate hydrogen;

[0073] S13. Hydrogen, a small part of water, a small amount of catalyst, and promoter particles are discharged from the overflow port 13 and enter the liquid storage tank 30. The hydrogen is temporarily stored above the liquid level of the liquid storage tank 30; the first solution after the swirl ends is discharged from the underflow port 15 and returned to the liquid storage tank 30;

[0074] S14. Repeat steps S2 - S3 until the entire reaction ends;

[0075] S5. After reacting for 4 h, the hydrogen is discharged from the hydrogen outlet 34 and enters the subsequent treatment process through the hydrogen output pipeline 341.

[0076] The hydrogen production capacity and total energy consumption of this embodiment are shown in Table 1.

[0077] Comparative Example 1: Hydrogen production by ultrasonic piezoelectric alone

[0078] The difference between this comparative example and Example 1 is that the first solution is directly placed in the swirl ultrasonic coupling reactor 10, and the ultrasonic generating device 20 is turned on (ultrasonic frequency 28 KHz, ultrasonic power 120 w);

[0079] After reacting for 4 h, the hydrogen is discharged from the hydrogen outlet 34 and enters the subsequent treatment process through the hydrogen output pipeline 341.

[0080] The hydrogen production capacity and total energy consumption of this comparative example are shown in Table 1.

[0081] Comparative Example 2: Hydrogen production by ultrasonic piezoelectricity alone

[0082] The difference between this comparative example and Example 1 is that the first solution is directly placed in the swirling ultrasonic coupling reactor 10, and the ultrasonic generating device 20 (ultrasonic frequency 40KHz, ultrasonic power 360w) is turned on;

[0083] After reacting for 4h, hydrogen gas is discharged from the hydrogen gas outlet 34 and enters the subsequent treatment process through the hydrogen output pipeline 341.

[0084] The hydrogen production capacity and total energy consumption of this comparative example are shown in Table 1.

[0085] Comparative Example 3: Hydrogen production by swirling piezoelectricity alone

[0086] The difference between this comparative example and Example 1 is that the ultrasonic generating device 20 is not turned on, and the first solution is controlled to enter the swirling ultrasonic coupling reactor 10 along the three tangential inlets 12 at a speed of 3.3m / s respectively;

[0087] After reacting for 4h, hydrogen gas is discharged from the hydrogen gas outlet 34 and enters the subsequent treatment process through the hydrogen output pipeline 341.

[0088] The hydrogen production capacity and total energy consumption of this comparative example are shown in Table 1.

[0089] Comparative Example 4: Hydrogen production by swirling piezoelectricity alone

[0090] The difference between this comparative example and Example 1 is that the ultrasonic generating device 20 is not turned on, and the first solution is controlled to enter the swirling ultrasonic coupling reactor 10 along the three tangential inlets 12 at a speed of 6.6m / s respectively;

[0091] After reacting for 4h, hydrogen gas is discharged from the hydrogen gas outlet 34 and enters the subsequent treatment process through the hydrogen output pipeline 341.

[0092] The hydrogen production capacity and total energy consumption of this comparative example are shown in Table 1.

[0093] Table 1. Comparison of hydrogen production capacity and energy consumption of hydrogen production systems by ultrasonic alone, swirling alone and swirling coupled with ultrasonic piezoelectricity

[0094]

[0095] It can be seen from the data in Table 1 that under the conditions of ultrasonic frequency 28KHz and ultrasonic power 120w, ultrasonic excitation of MoS alone 2 The hydrogen production amount is only 50μmol / g / h. By enhancing the ultrasonic frequency and power, increasing the ultrasonic power and frequency to 40KHz and 360w respectively, the hydrogen production capacity only increases to 70μmol / g / h, and the energy consumption further increases.

[0096] Under a separate swirling flow-excited piezoelectric hydrogen production system, when the inlet flow rate is 3.3 m / s, the hydrogen production capacity is only 120 μmol / g / h, and the energy consumption is 0.45 kwh; when the flow field flow rate is increased and the speed of the first solution flowing into the swirling flow ultrasonic coupling reactor 10 is increased to 6.6 m / s, the hydrogen production capacity is increased to 215 μmol / g / h, and the energy consumption is increased to 0.95 kwh.

[0097] Under the action of swirling flow coupling ultrasonic, the ultrasonic frequency is 28 KHz, the power is 120 w, the swirling flow inlet flow rate is 3.3 m / s, the hydrogen production capacity is 220 μmol / g / h, and the total energy consumption is only 0.57 kwh. Its energy consumption is the sum of the energy consumptions of Comparative Example 1 and Comparative Example 3, but the hydrogen production capacity is much greater than the sum of Comparative Example 1 and Comparative Example 3, indicating that the method of the present invention can effectively solve the problems of high energy consumption and low efficiency of the current ultrasonic excitation piezoelectric effect; compared with the high flow rate (6.6 m / s) of Comparative Example 4, the hydrogen production capacity of Example 1 is higher than that of Comparative Example 4, and its 4-hour energy consumption is much lower than that of Comparative Example 4, further indicating that the method of the present invention can achieve high hydrogen production efficiency under the conditions of low flow rate (swirling flow rate: the flow rate of the first solution flowing into the swirling flow ultrasonic coupling reactor) and low frequency (ultrasonic oscillation + swirling flow oscillation) through swirling flow coupling ultrasonic piezoelectric hydrogen production.

[0098] The above embodiments are only for illustrating the technical concept and characteristics of the present invention, and the purpose is to enable those who are familiar with this technology to understand the content of the present invention and implement it accordingly, and it cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A swirl oscillation coupled ultrasonic piezoelectric hydrogen production device, characterized in that: include A cyclonic ultrasonic coupling reactor comprises a first part and a second part located below the first part and connected to the first part, wherein the first part is a cylindrical section, and three tangential inlets are evenly distributed circumferentially on the side wall near the top, and an overflow port is provided at the top; tangential inlet pipelines are provided at the three tangential inlets, and an overflow pipeline is provided at the overflow port; the second part is a conical section, and an underflow port is provided at the bottom, and an underflow pipeline is provided at the underflow port; An ultrasonic generating device, comprising an ultrasonic vibrating rod and an ultrasonic generator, wherein the ultrasonic generator and the ultrasonic vibrating rod are electrically connected, and the ultrasonic vibrating rod is fixed inside a cyclonic ultrasonic coupling reactor; A liquid storage tank, wherein a liquid outlet pipeline is provided at the lower part thereof, and a first reflux port and a second reflux port are provided at the upper part thereof; the liquid outlet pipeline is connected to the tangential inlet pipeline; the overflow pipeline is connected to the first reflux port, and the underflow pipeline is connected to the second reflux port; The centrifugal pump is arranged on the liquid outlet pipeline and is used to pump the liquid in the liquid storage tank into the cyclonic ultrasonic coupling reactor.

2. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device according to claim 1 is characterized in that: The tangential inlet is rectangular.

3. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device according to claim 1 is characterized in that: The ultrasonic vibration rod is fixed on the central axis of the cyclonic ultrasonic coupling reactor through three identical brackets.

4. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device according to claim 2, characterized in that: The three tangential inlets are 50 mm to 100 mm long and 100 mm to 200 mm wide, and are all inclined downward by 0° to 60°. The three tangential inlets are evenly distributed on the side wall of the cyclonic ultrasonic coupling reactor at an angle of 120°.

5. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device according to claim 4, characterized in that: The three tangential inlets are 50 mm long and 100 mm wide, and are all inclined downward at 45°. The three tangential inlets are evenly distributed on the side wall of the cyclonic ultrasonic coupling reactor at an angle of 120°.

6. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device according to claim 1, characterized in that: The diameter of the cylindrical section of the first part is DN250~DN500, and the length is 200mm~400mm; the cone angle of the conical section of the second part is 6°~10°, the overflow port diameter is 100mm~150mm, and the bottom flow port diameter is 100mm~150mm; the diameter of the ultrasonic vibration rod is 50~80mm, the length is 200mm-400mm, and the material is SUS304.

7. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device according to claim 6, characterized in that: The diameter of the cylindrical section of the first part is DN250 and the length is 370mm; the cone angle of the conical section of the second part is 7°, the overflow port diameter is 100mm, and the bottom flow port diameter is 100mm; the ultrasonic vibration rod has a diameter of 52mm and a length of 300mm.

8. The swirl oscillation coupled ultrasonic piezoelectric hydrogen production device according to claim 1, characterized in that: The ultrasonic power of the ultrasonic vibration rod is 120-1800w, and the ultrasonic frequency is 20KHz-40KHz.

9. A method for producing hydrogen by swirl oscillation coupled ultrasonic piezoelectricity, characterized in that: The cyclone-coupled ultrasonic piezoelectric hydrogen production device according to any one of claims 1 to 8 comprises the following steps: S1. The piezoelectric catalyst particles and the promoter particles are evenly dispersed in water to obtain a first solution, which is placed in a liquid storage tank; an ultrasonic generator is turned on; S2. The first solution in the liquid storage tank is respectively introduced into the cyclone ultrasonic coupling reactor along the three tangential inlets at a first speed by a centrifugal pump, so as to form a strong three-dimensional rotating flow field in the cyclone ultrasonic coupling reactor, and the piezoelectric effect of the piezoelectric catalyst is stimulated by the combined action of the cyclone oscillation and the ultrasonic oscillation to generate hydrogen; S3. Hydrogen, a small amount of water, a small amount of catalyst, and catalyst promoter particles are discharged from the overflow port and enter the liquid storage tank. The hydrogen is temporarily stored above the liquid surface of the liquid storage tank; the first solution after the swirl is discharged from the bottom flow port and returned to the liquid storage tank; S4. Repeat steps S2 to S3 until the entire reaction is completed.

10. The method for producing hydrogen by swirl oscillation coupled ultrasonic piezoelectricity according to claim 9, characterized in that: The first speed is 1 m / s to 8 m / s.

Images