CN116121813A - Nano bubble generating device, electrocatalytic reaction system and method thereof - Google Patents
Nano bubble generating device, electrocatalytic reaction system and method thereof Download PDFInfo
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- CN116121813A CN116121813A CN202211543704.4A CN202211543704A CN116121813A CN 116121813 A CN116121813 A CN 116121813A CN 202211543704 A CN202211543704 A CN 202211543704A CN 116121813 A CN116121813 A CN 116121813A
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Abstract
The invention relates to the technical field of electrocatalysis, in particular to a nano bubble generating device, an electrocatalytic reaction system and a method thereof. The nano bubble generating device comprises a gas storage cabin, an electrolyte tank and rotatable sleeves, wherein the sleeves extend from the gas storage cabin to the electrolyte tank, the sleeves are of hollow structures, a plurality of first air holes are formed in the side walls of the parts in the gas storage cabin, a plurality of hollow paddles are arranged on the side walls of the parts in the electrolyte tank, the inner cavities of the hollow paddles are communicated with the inner cavities of the sleeves, and a plurality of second air holes are formed in the walls of each hollow paddle. The nano bubble generating device can improve the solubility of carbon dioxide in the flue gas generated by coal chemical industry/coal electricity in the electrolyte, thereby improving the electrolytic catalysis efficiency of the carbon dioxide.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a nano bubble generating device, an electrocatalytic reaction system and a method thereof.
Background
The flow rate of the flue gas generated in the coal electricity/coal chemical industry is large, but the content of carbon dioxide in the flue gas is very low, namely only about 10vol%, and when the flue gas is used as raw material gas for electrocatalytic reaction after dust removal, the flue gas is firstly introduced into electrolyte aqueous solution, but the solubility of the carbon dioxide in water at normal temperature is only 33mmol/L, and the solubility is further reduced along with the rise of the temperature, so that in the electrocatalytic conversion process of the carbon dioxide, the electrode catalytic material is mainly covered by water molecules in electrolyte, and only a small part of dissolved carbon dioxide molecules are catalyzed to form high-added-value products.
At present, two main methods are adopted around the electrocatalytic conversion technology of carbon dioxide digestion in coal electricity/coal chemical industry flue gas and solving the problem of low carbon dioxide solubility in aqueous electrolyte, wherein the first method is to pre-mix the flue gas with the electrolyte in a pressurizing mode and then to introduce the flue gas into an electrocatalytic conversion device for catalytic reaction, although the method can increase the solubility of carbon dioxide in the electrolyte to a certain extent, the flue gas pressurization usually needs a special pressurizing device, and the carbon dioxide gas can be re-separated out along with the gradual reduction of the pressure in the electrocatalytic reaction process. The second method is to add a spray tower device before the electrocatalytic reaction device, the flue gas is introduced from the bottom of the tower, the electrolyte is sprayed from the top of the tower and is discharged down, so that the contact area of the gas and the liquid is increased, the solubility of carbon dioxide in the flue gas in the electrolyte is improved, and finally the conversion efficiency of the carbon dioxide in the electrocatalytic reaction process is improved.
Disclosure of Invention
The invention aims at overcoming the defects that carbon dioxide in coal electricity/coal chemical industry flue gas in the prior art is low in solubility, cannot be completely absorbed by electrolyte and can be separated out again, so that the efficiency of an electrocatalytic reaction is reduced, and therefore provides a nano bubble generating device, an electrocatalytic reaction system and a method thereof. The nano bubble generating device is provided with the hollow sleeve, and the hollow sleeve can carry out nanocrystallization on the input dust-removed and purified flue gas under the rotation action, so that nano bubble electrolyte is obtained, and the solubility of carbon dioxide in the electrolyte is further improved; the nano bubble generating device and the roll-type electrocatalytic reaction device are combined to form an electrocatalytic reaction system, so that the electrolysis efficiency of the nano bubble electrolyte output from the nano bubble generating device can be further improved.
In order to achieve the above object, a first aspect of the present invention provides a nano bubble generating device, which includes a gas storage compartment, an electrolyte tank, and a rotatable sleeve, wherein the sleeve extends from the gas storage compartment to the electrolyte tank, the sleeve is of a hollow structure, a plurality of first air holes are formed in a side wall of a portion located in the gas storage compartment, a plurality of hollow blades are formed in a side wall of a portion located in the electrolyte tank, an inner cavity of each hollow blade is communicated with an inner cavity of the sleeve, and a plurality of second air holes are formed in a wall of each hollow blade.
Preferably, the device further comprises a motor, a transmission shaft and a connecting part which are sequentially connected, wherein the connecting part is connected with the sleeve, and the sleeve is driven to rotate by the motor.
Preferably, the aperture of the second air hole on the hollow blade is 0.1-0.5mm.
Preferably, the gas storage cabin is provided with a flue gas inlet for conveying the dust-removed and purified flue gas into the gas storage cabin.
Preferably, the electrolyte tank is provided with an electrolyte inlet and a nano bubble electrolyte outlet, electrolyte for absorbing carbon dioxide in the flue gas is injected into the electrolyte tank through the electrolyte inlet, and nano bubble electrolyte containing carbon dioxide nano bubbles is output through the nano bubble electrolyte outlet.
The second aspect of the invention provides an electrocatalytic reaction system, which comprises the nano bubble generating device and an electrocatalytic reaction device, wherein the nano bubble generating device is used for mixing flue gas subjected to dust removal and purification with electrolyte to obtain nano bubble electrolyte containing carbon dioxide nano bubbles, and the electrocatalytic reaction device is used for carrying out electrocatalytic reaction on the nano bubble electrolyte.
Preferably, the electrocatalytic reaction device is a roll-type electrocatalytic reaction device.
Preferably, the roll-type electrocatalytic reaction device comprises a cathode, a proton exchange membrane and an anode, wherein the proton exchange membrane is positioned between the cathode and the anode.
Preferably, a nano bubble electrolyte flow channel is formed inside the cathode, and the nano bubble electrolyte flow channel is used for containing the nano bubble electrolyte from the nano bubble generating device; an anolyte flow channel is formed between the anode and the proton exchange membrane, and is used for containing anolyte.
Preferably, the cathode comprises a cathode substrate, and a Sn component and/or a Bi component deposited on the cathode substrate; more preferably, the cathode substrate is an iron or nickel mesh.
Preferably, the anode comprises an anode substrate and a catalyst coating coated on the anode substrate; more preferably, the active component in the catalyst coating is Pt and/or C.
In a third aspect, the invention provides a method of electrocatalytic reduction of carbon dioxide to produce a chemical, the method comprising: mixing the flue gas after dust removal and purification with electrolyte in a nano bubble generating device to obtain nano bubble electrolyte containing carbon dioxide nano bubbles, and then conveying the nano bubble electrolyte into the electrocatalytic reaction device for electrocatalytic reaction.
Through the technical scheme, the nano bubble generating device can effectively improve the solubility of carbon dioxide in the flue gas after dust removal and purification in electrolyte, and forms an electrocatalytic system by being combined with a coiled electrocatalytic reaction device, and the resistance in the electrolytic reaction process is reduced by regulating and controlling the distance between a cathode and an anode, so that the current density is higher, and the speed and the efficiency of the electrocatalytic reaction of the carbon dioxide are further improved.
Drawings
FIG. 1 is a nanobubble generating device;
FIG. 2 is a roll-to-roll electrocatalytic reaction apparatus.
Description of the reference numerals
1, an electric motor; 2, a transmission shaft; 3, an air storage cabin; 4, a flue gas inlet after dust removal and purification; 5 an electrolyte tank; 6 hollow paddles; 7, an electrolyte inlet; 8 nanometer bubble electrolyte outlet; 9 connecting parts; 10 sleeves; an anode 11; a 12 cathode; 13 proton exchange membrane; 14 a bracket; 15 anolyte flow channels; a 16 nanometer bubble electrolyte flow channel.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise indicated, terms of orientation or positional relationship such as "upper, lower, left, right" and the like are used based on the orientation or relative positional relationship shown in the drawings to describe the present application only for convenience of simplified description, and do not indicate that the apparatus or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present application.
Furthermore, unless explicitly specified and limited otherwise, the term "coupled" is to be construed broadly and may be, for example, fixedly coupled, detachably coupled, or integrally coupled; can be mechanically or electrically connected; either directly or indirectly through intermediaries, or in communication with each other. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art as the case may be.
In the invention, the flue gas is flue gas generated by a coal-fired power plant or a coal-fired chemical plant.
In the invention, the carbon dioxide content in the flue gas is more than 10%.
The invention accelerates the movement of particles by utilizing the carbon dioxide gas in the flue gas under the rotation action, so that the carbon dioxide gas is in a high-energy state, and then passes through a plurality of small holes to be extruded and crushed, so that the carbon dioxide gas is in a nano state, and the solubility of the carbon dioxide in the electrolyte is increased.
The first aspect of the present invention provides a nano bubble generating device, which is characterized in that the device comprises a gas storage cabin 3, an electrolyte tank 5 and a rotatable sleeve 10, wherein the sleeve 10 extends from the gas storage cabin 3 to the electrolyte tank 5, the sleeve 10 is of a hollow structure, a plurality of first air holes are formed in the side wall of a part located in the gas storage cabin 3, a plurality of hollow blades 6 are arranged on the side wall of a part located in the electrolyte tank 5, the inner cavity of each hollow blade 6 is communicated with the inner cavity of the sleeve 10, and a plurality of second air holes are formed in the wall of each hollow blade 6.
In the invention, before the flue gas generated by coal electricity or coal chemical industry is introduced into the nano bubble generating device, the flue gas needs to be subjected to dust removal and purification, and the dust removal and purification mainly removes dust in the flue gas. The method used for dust removal and purification in the invention is a conventional technical means in the field.
In the present invention, in order to facilitate and efficiently operate the sleeve 10 in the nano bubble generating apparatus, the apparatus further comprises a motor 1, a transmission shaft 2, and a connection member 9 sequentially connected, the connection member 9 being connected with the sleeve 10.
In the invention, the connecting part 9 is in a solid structure in a preferable condition, so that the balance of the transmission shaft 2 can be improved, gas can enter the sleeve 10 stably, and the solubility of carbon dioxide gas can be improved.
In the invention, the gas storage cabin 3 is provided with a smoke inlet 4 for conveying dust-removed and purified smoke into the gas storage cabin 3.
In the present invention, the flue gas introduced into the gas storage compartment 3 is introduced into the sleeve 10 through the first gas holes, and in a specific embodiment, the density of the holes of the first gas holes is 10-100 holes/cm 2 . In a preferred embodiment, the first air holes have a hole density of 20 to 80 holes/cm 2 For example 20 pieces/cm 2 30 pieces/cm 2 40 pieces/cm 2 50 pieces/cm 2 60 pieces/cm 2 70/cm 2 Or 80/cm 2 。
In the present invention, the motor 1 drives the sleeve 10 to rotate, and in a specific embodiment, the rotation speed of the sleeve 10 is 100-500r/min, for example, may be 100r/min, 200r/min, 250r/min, 300r/min, 400r/min or 500r/min.
The flue gases entering the sleeve 10 will then move vigorously with the drive shaft 2 rotating continuously and enter the hollow blades 6. In the present invention, the hollow blades 6 may be symmetrically distributed on the side wall of the sleeve 10. In a preferred case, the hollow blade 6 is a rotatable blade.
In the present invention, the electrolyte tank 5 has an electrolyte inlet 7, and an electrolyte for absorbing carbon dioxide in the flue gas is injected into the electrolyte tank 5 through the electrolyte inlet 7.
The flue gas entering the hollow blade 6 enters the electrolyte tank 5 through the second air holes on the wall of the hollow blade 6 under the continuous rotation of the sleeve 10, and is dissolved with the electrolyte in the electrolyte tank 5 to obtain the nano bubble electrolyte containing the carbon dioxide nano bubbles.
In the invention, the second air hole is not too large or too small, and the air hole is too large to lead the discharged gas not to be nanocrystallized, so that the discharged gas cannot be fully dissolved, and the too small air hole can lead the carbon dioxide gas to be difficult in the discharging process, thereby influencing the dissolving speed and efficiency.
In the present invention, in a specific embodiment, the second air hole has a pore diameter of 0.1 to 5mm, for example, 0.1mm, 0.5mm, 1mm, 2mm, 3mm, 4mm or 5mm.
In the present invention, the electrolyte tank 5 has a nanobubble electrolyte outlet 8, and the nanobubble electrolyte containing carbon dioxide nanobubbles is outputted through the nanobubble electrolyte outlet 8.
In one embodiment, the nano bubble generating device comprises a motor 1, a transmission shaft 2, a connecting part 9, a sleeve 10, a gas storage cabin 3 and a nano bubble electrolyte tank 5, wherein the gas storage cabin 3 is provided with a flue gas inlet 4, the electrolyte tank 5 is provided with an electrolyte inlet 7 and a nano bubble electrolyte outlet 8, one end of the transmission shaft 2 is connected with the motor 1, the other end of the transmission shaft is connected with the connecting part 9, the connecting part 9 is of a solid structure, the other end of the connecting part 9 is connected with the sleeve 10, the sleeve 10 is of a hollow structure, the sleeve 10 extends from the gas storage cabin 3 to the electrolyte tank 5, 8 first air holes are formed in the side wall of the part, located in the electrolyte tank 5, of each hollow blade 6, 16 second air holes are formed in the wall of each hollow blade 6, and the aperture of each second air hole is 0.3mm.
In another embodiment, the nano bubble generating device comprises a motor 1, a transmission shaft 2, a connecting part 9, a sleeve 10, a gas storage cabin 3 and a nano bubble electrolyte tank 5, the gas storage cabin 3 is provided with a flue gas inlet 4, the electrolyte tank 5 is provided with an electrolyte inlet 7 and a nano bubble electrolyte outlet 8, one end of the transmission shaft 2 is connected with the motor 1, the other end of the transmission shaft is connected with the connecting part 9, the connecting part 9 is of a solid structure, the other end of the connecting part 9 is connected with the sleeve 10, the sleeve 10 is of a hollow structure, the sleeve 10 extends from the gas storage cabin 3 to the electrolyte tank 5, 12 first air holes are formed in the side wall of the part of the sleeve 10 located in the gas storage cabin 3, 12 hollow paddles 6 are arranged on the side wall of the part located in the electrolyte tank 5, 22 second air holes are formed in the wall of each hollow paddle 6, and the aperture of the second air holes is 3mm.
In the present invention, in a specific embodiment, KHCO is contained in the electrolytic bath 5 3 And/or K 2 CO 3 A solution.
The second aspect of the invention provides an electrocatalytic reaction system, which comprises the nano bubble generating device and an electrocatalytic reaction device, wherein the nano bubble generating device is used for mixing flue gas subjected to dust removal and purification with electrolyte to obtain nano bubble electrolyte containing carbon dioxide nano bubbles, and the electrocatalytic reaction device is used for carrying out electrocatalytic reaction on the nano bubble electrolyte.
In the present invention, the nanobubble generating device and the electrocatalytic reaction device may be connected in a conventional manner in the art. The connection may be made, for example, in the form of a pipe plus a circulation pump.
In a preferred embodiment of the present invention, the electrocatalytic reaction device is a roll-to-roll electrocatalytic reaction device. The distance between the anode and the cathode of the roll-type electrocatalytic reaction device is adjustable and smaller, so that ohmic resistance of the electrocatalytic reaction can be greatly reduced, current density is higher, electrocatalytic efficiency is higher, and the volume of the device is greatly reduced due to the roll-type structure.
In the present invention, the roll-type electrocatalytic reaction device comprises a cathode 12, a proton exchange membrane 13 and an anode 11, wherein the proton exchange membrane 13 is positioned between the cathode 12 and the anode 11.
In the present invention, in a specific embodiment, the cathode 12 includes a cathode substrate, which is an iron or nickel net, and a Sn component and/or a Bi component deposited on the cathode substrate.
In the present invention, in a specific embodiment, the method for preparing the cathode 12 comprises: taking an iron screen or a nickel screen as a substrate, adopting an electrodeposition method, and taking deionized water as a solvent to prepare 100-1000mL of SnCl with the concentration of 0.05-0.1mol/L 4 100-1000mL of deposition solution and 0.25-0.45mol/L of H 3 BO 4 The deposition solution is then electrochemically deposited at a voltage in the range of 1-2.5V.
In the present invention, in a specific embodiment, the anode 11 includes an anode substrate and a catalyst coating layer coated on the anode substrate, wherein an active component in the catalyst coating layer is Pt and/or C.
In the present invention, in a specific embodiment, the preparation method of the anode 11 comprises: pt and/or C is/are taken as an anode catalyst, added into ethanol or isopropanol solution to prepare solution with concentration of 0.1-1mg/mL and volume of 100-1000mL, then nafion solution with mass fraction of 5% is added into the solution for 10-30ul/mL, ultrasonic treatment is carried out for 10-30min to form uniform solution, and the obtained uniform solution is utilized to form a uniform spray coating on the surface of stainless steel.
In the present invention, a nano bubble electrolyte flow passage 16 is formed inside the cathode 12, the nano bubble electrolyte flow passage 16 being for receiving the nano bubble electrolyte from the nano bubble generating device; an anolyte flow channel 15 is formed between the anode 11 and the proton exchange membrane 13, and the anolyte flow channel 15 is used for containing anolyte.
In the present invention, in the specific embodiment, KHCO is contained in the anolyte flow passage 15 3 And/or K 2 CO 3 A solution.
In the invention, the nano bubble electrolyte containing carbon dioxide nano bubbles formed in the nano bubble generating device is output from the nano bubble electrolyte outlet 8 and enters the nano bubble electrolyte flow channel 16 of the roll-type electrocatalytic reaction device, hydrogen is continuously generated at the cathode, and the carbon dioxide in the nano bubble electrolyte reacts with the hydrogen to generate formic acid.
In the present invention, in a specific embodiment, the operating voltage of the roll type electrocatalytic reaction device may be 1.6-2.0V, for example, 1.6V, 1.7V, 1.8V, 1.9V or 2.0V.
In the present invention, the distance between the cathode 12 and the anode 11 affects the electrocatalytic reaction efficiency, and thus, the distance between the cathode 12 and the anode 11 needs to be set in a proper range. In the present invention, in a specific embodiment, the distance between the cathode 12 and the anode 11 is 0.1 to 1cm, and may be, for example, 0.1cm, 0.2cm, 0.3cm, 0.4cm, 0.5cm, 0.6cm, 0.7cm, 0.8cm, 0.9cm, or 1.0cm.
In order to improve the stability of the roll type electrocatalytic reaction device and flexibly adjust the interval between the anode and the cathode, the invention can be provided with a bracket in the roll type electrocatalytic reaction device. In a preferred embodiment, a bracket is provided in the anolyte flow passage 15, and both ends of the bracket are connected to the anode 11 and the proton exchange membrane 13, respectively.
In a preferred embodiment of the present invention, two or more of the roll-type electrocatalytic reaction devices may be assembled together in parallel in sequence to form a single combined type electrocatalytic reaction device.
In a specific embodiment, the electrocatalytic reaction system comprises a nano bubble generating device and an electrocatalytic reaction device, wherein the nano bubble generating device comprises a motor 1, a transmission shaft 2, a connecting part 9, a sleeve 10, a gas storage cabin 3 and a nano bubble electrolyte tank 5, the gas storage cabin 3 is provided with a flue gas inlet 4, the electrolyte tank 5 is provided with an electrolyte inlet 7 and a nano bubble electrolyte outlet 8, one end of the transmission shaft 2 is connected with the motor 1, the other end of the transmission shaft is connected with the connecting part 9, the connecting part 9 is of a solid structure, the other end of the connecting part 9 is connected with the sleeve 10, the sleeve 10 is of a hollow structure, the sleeve 10 extends from the gas storage cabin 3 to the electrolyte tank 5, 12 first air holes are formed in the side wall of the part of the sleeve 10 located in the gas storage cabin 3, 12 hollow blades 6 are arranged in the side wall of the part located in the electrolyte tank 5, 22 second air holes are formed in the wall of each hollow blade 6, and the aperture of the second air holes is 0.3mm.
The electrocatalytic reaction device is a roll-type electrocatalytic reaction device, the roll-type electrocatalytic reaction device comprises a cathode 12, a proton exchange membrane 13 and an anode 11, the proton exchange membrane 13 is positioned between the cathode 12 and the anode 11, a nano bubble electrolyte flow channel 16 is formed in the cathode 12, and the nano bubble electrolyte flow channel 16 is used for containing the nano bubble electrolyte from the nano bubble generation device; an anolyte flow channel 15 is formed between the anode 11 and the proton exchange membrane 13, and the anolyte flow channel 15 is used for containing anolyte; wherein the cathode 12 includes an iron net and a Sn component deposited on the iron net, and the anode 11 includes stainless steel and Pt coated on the stainless steel.
In another specific embodiment, the electrocatalytic reaction system comprises the nano bubble generating device and the electrocatalytic reaction device, wherein the nano bubble generating device comprises a motor 1, a transmission shaft 2, a connecting part 9, a sleeve 10, a gas storage cabin 3 and a nano bubble electrolyte tank 5, the gas storage cabin 3 is provided with a flue gas inlet 4, the electrolyte tank 5 is provided with an electrolyte inlet 7 and a nano bubble electrolyte outlet 8, one end of the transmission shaft 2 is connected with the motor 1, the other end of the transmission shaft is connected with the connecting part 9, the connecting part 9 is of a solid structure, the other end of the connecting part 9 is connected with the sleeve 10, the sleeve 10 is of a hollow structure, the sleeve 10 extends from the gas storage cabin 3 to the electrolyte tank 5, 8 first air holes are formed in the side wall of the part of the sleeve 10 located in the gas storage cabin 3, 8 hollow blades 6 are arranged in the side wall of the part located in the electrolyte tank 5, 16 second air holes are formed in the wall of each hollow blade 6, and the aperture of the second air holes is 2mm.
The electrocatalytic reaction device is a roll-type electrocatalytic reaction device, the roll-type electrocatalytic reaction device comprises a cathode 12, a proton exchange membrane 13 and an anode 11, the proton exchange membrane 13 is positioned between the cathode 12 and the anode 11, a nano bubble electrolyte flow channel 16 is formed in the cathode 12, and the nano bubble electrolyte flow channel 16 is used for containing the nano bubble electrolyte from the nano bubble generation device; an anolyte flow channel 15 is formed between the anode 11 and the proton exchange membrane 13, and the anolyte flow channel 15 is used for containing anolyte; wherein the cathode 12 includes an iron net and a Bi component deposited on the iron net, and the anode 11 includes stainless steel and Pt coated on the stainless steel.
The system for improving the electrocatalytic efficiency of carbon dioxide in flue gas according to the invention is further described below by way of examples. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below are commercially available unless otherwise specified.
Example 1
The flue gas used in the invention is the flue gas generated by a coal-fired power plant, wherein the carbon dioxide content is 10%.
This embodiment is implemented in an electrocatalytic system as shown in fig. 1 and 2, comprising: the nanobubble generating device shown in fig. 1 and the roll-type electrocatalytic reaction device shown in fig. 2. The nano bubble generating device comprises a motor 1, a transmission shaft 2, a connecting part 9, a sleeve 10, a gas storage cabin 3 and an electrolyte tank 5, wherein one end of the transmission shaft 2 is connected with the motor 1, the other end of the transmission shaft is connected with the connecting part 9, the other end of the connecting part 9 is connected with the sleeve 10, the connecting part 9 is of a solid structure, the sleeve 10 is of a hollow structure, the sleeve 10 extends from the gas storage cabin 3 to the electrolyte tank 5, 16 first air holes are formed in the side wall of the part of the sleeve 10, which is positioned in the gas storage cabin 3, 16 hollow paddles 6 are arranged on the side wall of the part, which is positioned in the electrolyte tank 5, of each hollow paddle 6, and 18 second air holes are formed in the wall of each hollow paddle 6. Firstly, dust removal and purification are carried out on smoke, the rotating speed of a transmission shaft 2 is set to be 500r/min, the motor 1 drives the sleeve 10 to rotate, the dust removal and purification gas enters the gas storage cabin 3 through the smoke inlet 4 and sequentially passes through a first air hole, a hollow blade 6 and a second air hole, the aperture of the second air hole is 0.5mm, and the smoke enters the electrolyte tank 5 after being discharged from the second air hole and is fused with electrolyte in the electrolyte tank to obtain the nano bubble electrolyte containing carbon dioxide nano bubbles.
The roll-type electrocatalytic reaction device comprises a cathode 12, a proton exchange membrane 13 and an anode 11, wherein the distance between the cathode 12 and the anode 11 is 1cm, a nano bubble electrolyte flow channel 16 is formed in the cathode 12, an anolyte flow channel 15 is formed between the anode 11 and the proton exchange membrane 13, the cathode 12 comprises an iron net and Sn deposited on a pasting net, and the anode 11 comprises stainless steel and a catalyst coating containing Pt. Wherein, the nano bubble generating device is connected with the roll type electrocatalytic reaction device, so that the nano bubble electrolyte containing carbon dioxide nano bubbles is output from the nano bubble electrolyte outlet 8 and enters the nano bubble electrolyte flow channel 16, a voltage of 1.8V is introduced, and the carbon dioxide in the nano bubble electrolyte containing carbon dioxide nano bubbles reacts with the hydrogen generated by the cathode for 100 hours to generate formic acid, the formic acid content is 5mmol/L, and the current density is 300mA/cm 2 。
Example 2
The electrocatalytic system used and the fumes used were the same as in example 1, except that the nanobubblesThe aperture of the second air hole in the generating device is 0.1mm, the formic acid content is 8mmol/L, and the current density is 400mA/cm 2 。
Example 3
The electrocatalytic system used and the flue gas used were the same as in example 1, except that the cathode 12 in the roll-type electrocatalytic reaction apparatus comprised an iron mesh and Bi deposited on a decal. Formic acid content of 6.1mmol/L and current density of 350mA/cm 2 。
Comparative example 1
Based on the embodiment 1, the system does not comprise a nano bubble generating device, directly introduces the flue gas after dust removal and purification into a nano bubble electrolyte flow channel 16 in a coiled electrocatalytic reaction device, and enables carbon dioxide in the flue gas to react with hydrogen generated by a cathode to generate formic acid, wherein the content of the formic acid is 1mmol/L, and the current density is 160mA/cm 2 。
Comparative example 2
On the basis of example 1, the sleeve 10 does not rotate with the motor 1. Formic acid content of 1mmol/L and current density of 160mA/cm 2 。
As can be seen from the formic acid content and the current density in the examples 1-3 and the comparative examples 1-2, the nano bubble generating device can improve the solubility of carbon dioxide in the electrolyte in the flue gas after dust removal and purification and improve the electrocatalytic efficiency of nano carbon dioxide.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. The utility model provides a nanometer bubble generating device, its characterized in that, the device includes gas storage cabin (3), electrolyte groove (5) and rotatable sleeve pipe (10), sleeve pipe (10) follow gas storage cabin (3) extend to electrolyte groove (5), just sleeve pipe (10) are hollow structure, are located offer a plurality of first gas pocket on the lateral wall of the part in gas storage cabin (3), be located be provided with a plurality of cavity paddle (6) on the lateral wall of the part in electrolyte groove (5), the inner chamber of cavity paddle (6) with the inner chamber intercommunication of sleeve pipe (10), every a plurality of second gas pocket has been offered on the wall of cavity paddle (6).
2. The nanobubble generating apparatus as claimed in claim 1, further comprising a motor (1), a transmission shaft (2) and a connecting member (9) connected in this order, wherein the connecting member (9) is connected to the sleeve (10), and the sleeve (10) is rotated by the motor (1).
3. The nanobubble generating apparatus as claimed in claim 1 or 2, wherein the second air hole on the hollow blade (6) has a pore diameter of 0.1-0.5mm.
4. A nanobubble generating device according to any one of claims 1-3, wherein the gas storage compartment (3) has a flue gas inlet (4) for delivering dust-cleaned flue gas into the gas storage compartment (3).
5. A nanobubble generating apparatus as claimed in any one of claims 1 to 3, wherein the electrolyte tank (5) has an electrolyte inlet (7) and a nanobubble electrolyte outlet (8), the electrolyte for absorbing carbon dioxide in the flue gas is injected into the electrolyte tank (5) through the electrolyte inlet (7), and the nanobubble electrolyte containing carbon dioxide nanobubbles is output through the nanobubble electrolyte outlet (8).
6. An electrocatalytic reaction system, characterized in that the system comprises the nano bubble generating device of claims 1-5, wherein the flue gas after dust removal and purification is mixed with electrolyte to obtain nano bubble electrolyte containing carbon dioxide nano bubbles, and an electrocatalytic reaction device for carrying out electrocatalytic reaction on the nano bubble electrolyte.
7. The system of claim 1, wherein the electrocatalytic reaction device is a roll-to-roll electrocatalytic reaction device.
8. The system of claim 7, wherein the roll-to-roll electrocatalytic reaction device comprises a cathode (12), a proton exchange membrane (13) and an anode (11), the proton exchange membrane (13) being located between the cathode (12) and the anode (11).
9. The system of claim 8, wherein a nanobubble electrolyte flow channel (16) is formed inside the cathode (12), the nanobubble electrolyte flow channel (16) for receiving the nanobubble electrolyte from the nanobubble generating device; an anolyte flow channel (15) is formed between the anode (11) and the proton exchange membrane (13), and the anolyte flow channel (15) is used for containing anolyte.
10. The system according to any one of claims 7-9, wherein the cathode (12) comprises a cathode substrate and a Sn component and/or a Bi component deposited on the cathode substrate;
preferably, the cathode substrate is an iron or nickel mesh.
11. The system according to any one of claims 7-10, characterized in that the anode (11) comprises an anode substrate and a catalyst coating coated on the anode substrate;
preferably, the active component in the catalyst coating is Pt and/or C.
12. A method for preparing a chemical by electrocatalytic reduction of carbon dioxide, the method being carried out in a system according to any one of claims 6 to 11, the method comprising: mixing the flue gas after dust removal and purification with electrolyte in a nano bubble generating device to obtain nano bubble electrolyte containing carbon dioxide nano bubbles, and then conveying the nano bubble electrolyte into the electrocatalytic reaction device for electrocatalytic reaction.
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| CN117443197A (en) * | 2023-12-22 | 2024-01-26 | 天津工业大学 | Method for offline cleaning MBR hollow fiber membrane by utilizing ozone micro-nano bubbles |
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| CN117443197A (en) * | 2023-12-22 | 2024-01-26 | 天津工业大学 | Method for offline cleaning MBR hollow fiber membrane by utilizing ozone micro-nano bubbles |
| CN117443197B (en) * | 2023-12-22 | 2024-03-29 | 天津工业大学 | Method for offline cleaning MBR hollow fiber membrane by utilizing ozone micro-nano bubbles |
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