CN111569803B - A device and method for plasma catalytic reforming of greenhouse gases - Google Patents
A device and method for plasma catalytic reforming of greenhouse gases Download PDFInfo
- Publication number
- CN111569803B CN111569803B CN202010402738.6A CN202010402738A CN111569803B CN 111569803 B CN111569803 B CN 111569803B CN 202010402738 A CN202010402738 A CN 202010402738A CN 111569803 B CN111569803 B CN 111569803B
- Authority
- CN
- China
- Prior art keywords
- cylinder
- reactor
- gas
- plasma
- greenhouse gases
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000005431 greenhouse gas Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000001833 catalytic reforming Methods 0.000 title claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 230000033001 locomotion Effects 0.000 claims abstract description 16
- 230000014759 maintenance of location Effects 0.000 claims abstract description 9
- 238000002407 reforming Methods 0.000 claims abstract description 7
- 230000002035 prolonged effect Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 59
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000010724 circulating oil Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000005389 magnetism Effects 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000000429 assembly Methods 0.000 abstract 3
- 230000000712 assembly Effects 0.000 abstract 3
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 239000012494 Quartz wool Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 108010063955 thrombin receptor peptide (42-47) Proteins 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
- B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
- B01J2219/0845—Details relating to the type of discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0883—Gas-gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The device comprises a reactor, wherein the reactor comprises a first cylinder and a second cylinder which are coaxially nested, inner electrodes connected with a pulse power supply are arranged on the axes of the two cylinders, a grounding outer electrode is arranged on the outer side surface of the second cylinder, and a catalyst is filled in a gap between the first cylinder and the second cylinder; a magnetic stirring plate vertical to the bottom surface of the reactor is arranged at the position, close to the bottom surface of the reactor, of the outer side surface of the first barrel, a plurality of electromagnetic assemblies matched with the magnetic stirring plate are arranged on the outer side surface of the second barrel, and the polarity of one end, far away from the first barrel, of the magnetic stirring plate is the same as that of one side, close to the second barrel, of the electromagnetic assemblies when the electromagnetic assemblies are electrified; according to the method, the magnetic stirring equipment is arranged at the bottom of the reactor, the magnetic field of the magnetic stirring equipment is fully utilized, the movement of charged particles in a discharge air gap is changed, the retention time of the charged particles in a discharge interval is prolonged, the reaction of methane and carbon dioxide is promoted, and the greenhouse gas reforming efficiency is improved.
Description
Technical Field
The disclosure relates to the technical field of greenhouse gas catalytic reforming, in particular to a device and a method for plasma catalytic reforming of greenhouse gas.
Background
The statements in this section merely provide background information related to the present disclosure and may not necessarily constitute prior art.
With the development and utilization of such fossil energy, a global greenhouse effect has emerged. The increasing content of carbon dioxide, methane, and other greenhouse gases is a major cause of global warming and is also a feedstock gas for the industrial production of syngas, olefins, and other high value chemicals. In the face of the long-standing greenhouse effect, the carbon dioxide, methane and other greenhouse gases are subjected to resource utilization and converted into more valuable chemicals and fuels, so that the greenhouse effect is relieved, the energy utilization of carbon-based small molecules is realized, and the method is a key scientific and technological problem which is urgently needed to be solved in national economy and social development.
The plasma is composed of neutral atoms, molecules, radicals, excited states, ions, and electrons. The resource utilization of inert gases such as methane, carbon dioxide and the like can be realized by adopting plasma for activation, so that the activation energy barrier of the reaction is reduced, and the reaction is promoted. The plasma catalysis combining the plasma and the catalyst can improve the energy conversion efficiency by utilizing the interaction and synergistic effect of the plasma and the catalyst, and has wide application prospect in the aspect of preparing raw material gases of synthesis gas, olefin and other high-value chemicals.
The Dielectric Barrier Discharge (DBD) has low energy consumption, uniform and stable Discharge and simple reactor structure, is suitable for plasma catalysis under atmospheric pressure, and can form interaction and synergistic effect with more catalysts such as Ni/Al2O3, Ag/Al2O3, Pt/Al2O3, Pd/Al2O3, Ni/SiO2, zeolite or metal organic framework and the like, thereby improving the yield and selectivity of high-value chemicals for reforming greenhouse gases. The packed bed DBD has high electric field strength and electron energy, and can generate more frequent electron impact ionization, excitation, decomposition and other plasma reactions, generate abundant charged particles, radicals and excited state particles, and activate plasma catalysis with higher energy efficiency. While the high voltage inner electrodes of DBD reactors are typically in the form of smooth metal rod electrodes, threaded electrodes and coil electrodes, the smooth metal rod electrodes being the most commonly used.
The inventor of the present disclosure finds that in the existing dielectric barrier discharge mode, the retention time of electrons in a discharge region is short, and rapid and efficient reforming of greenhouse gases cannot be achieved, that is, the reaction of methane and carbon dioxide is slow, and the consumed time is long; the existing smooth metal rod electrode generates less high-energy electrons, heat is not diffused in time, and the high-voltage inner electrode is cracked due to thermal expansion of the inner cylinder body.
Disclosure of Invention
In order to solve the defects of the prior art, the magnetic stirring equipment is arranged at the bottom of the reactor, the magnetic field of the magnetic stirring equipment is fully utilized, the movement of charged particles in a discharge air gap is changed, the retention time of the charged particles in a discharge interval is prolonged, the reaction of methane and carbon dioxide is promoted, and the greenhouse gas reforming efficiency is improved.
In order to achieve the purpose, the following technical scheme is adopted in the disclosure:
in a first aspect of the present disclosure, an apparatus for plasma catalytic reforming of greenhouse gases is provided.
A device for reforming greenhouse gas by plasma catalysis comprises a reactor, wherein the reactor comprises a first cylinder and a second cylinder which are coaxially nested, inner electrodes connected with a pulse power supply are arranged on the axes of the two cylinders, a grounding outer electrode is arranged on the outer side surface of the second cylinder, and a catalyst is filled in a gap between the first cylinder and the second cylinder;
the position that the lateral surface of first barrel is close to the reactor bottom surface is equipped with the magnetism stirring board that can follow the rotation of first barrel, and the lateral surface of second barrel is equipped with a plurality ofly and magnetism stirring board complex electromagnetic component, and the polarity that the one end of first barrel was kept away from to magnetism stirring board is the same with the polarity that is close to one side of second barrel when the electromagnetic component circular telegram.
As some possible realization modes, the inner electrode is an aluminum bar, and the surface of the aluminum bar is provided with a plurality of bulges.
As a further limitation, the protrusions are each in contact with the aluminum foil of the inner surface of the first barrel.
As some possible implementation manners, a plurality of magnetic stirring plates with the same angle are fixed on the outer side surface of the first cylinder along the circumferential direction, and the movement space of each magnetic stirring plate is a gap between the first cylinder and the second cylinder.
As some possible realization modes, the magnetic stirring plate is vertical to the bottom surface of the reactor.
As possible realization modes, the reactor also comprises an argon storage device, a carbon dioxide storage device and a methane storage device, wherein the argon storage device and the carbon dioxide storage device are respectively communicated with the first mass flow meter through pipelines, the methane storage device is communicated with the second mass flow meter through pipelines, the first mass flow meter and the second mass flow meter are respectively communicated with the gas premixing tank through pipelines, and the gas premixing tank is communicated with the gas inlet at the top of the reactor through a pipeline.
As possible realization modes, the bottom of the reactor is provided with an air outlet, the air outlet is sequentially communicated with a soap film flowmeter, a cold trap, a gas collecting box, an air pump and a gas chromatograph through pipelines, and the chromatograph is connected with a computer terminal.
As a further limitation, the system also comprises an oscilloscope, an air pump, a thermal infrared imager, a water pump and an alternating current power supply; the infrared thermal imager is used for acquiring real-time temperature data of the reactor and transmitting the real-time temperature data to the computer terminal; the heater is used for heating the circulating oil to provide a stable temperature condition, the water pump is used for enabling the circulating oil to reach a circulating state, and the alternating current power supply is used for providing power for the magnetic stirrer.
As some possible implementations, the grounding outer electrode is a stainless steel net covered on the outer surface of the second cylinder, and the stainless steel net is grounded through a capacitor.
As some possible implementations, the catalyst is a Ni-Al2O3 catalyst, and the Ni-Al2O3 catalyst is fixed with quartz wool.
A second aspect of the present disclosure provides a method of operating an apparatus for plasma catalytic reforming of greenhouse gases.
A method of operating an apparatus for plasma catalytic reforming of greenhouse gases using an apparatus for plasma catalytic reforming of greenhouse gases according to the first aspect of the present disclosure, comprising the steps of:
the pulse power supply is switched on, and the electromagnetic assembly is electrified;
before the greenhouse gas is catalytically reformed by the plasma, introducing argon into a gap between a first cylinder and a second cylinder of the reactor, and reducing the catalyst in argon discharge plasma;
methane gas and carbon dioxide gas in a preset proportion are introduced into a gap between a first cylinder and a second cylinder of the reactor, and discharge is carried out under the action of an inner electrode;
the movement of the magnetic stirring plate generates a magnetic field, the original movement path of the charged particles is changed under the action of the magnetic field, and the retention time of the charged particles in a discharge interval is prolonged.
Compared with the prior art, the beneficial effect of this disclosure is:
1. according to the device and the method disclosed by the disclosure, the magnetic stirring device is arranged at the bottom of the reactor, the magnetic field generated by the magnetic stirring device changes the motion of the charged particles in the discharge air gap, the original motion path of the charged particles is changed under the action of the magnetic field, the retention time of the charged particles in a discharge interval is increased, in addition, the resistance of metal is increased due to the magnetoresistance effect, the electric conduction capability is reduced, the energy loss of released high-energy electrons is reduced, and the collision reaction rate of the electrons and methane carbon dioxide is improved.
2. According to the device and the method, the high-voltage inner electrode is composed of a thorn-shaped aluminum rod and an aluminum foil tightly attached to the inner wall of the inner-layer quartz glass cylinder, and the thorn-shaped structure on the aluminum rod is tightly contacted with the aluminum foil. The electrode can obtain more high-energy electrons, enlarge the surface area of the electrode, enhance the reaction effect, reduce the heat loss at the same time, ensure that the generated heat can be diffused in time, and effectively avoid the inner glass cylinder from being cracked due to the thermal expansion of the high-voltage inner electrode.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for plasma catalytic reforming of greenhouse gases provided in embodiment 1 of the present disclosure.
Fig. 2 is a top view of a magnetic stirrer provided in embodiment 1 of the present disclosure.
1-argon gas cylinder; 2. a carbon dioxide cylinder; 3. a methane cylinder; 4. a DBD reactor; 5. a soap film flow meter; 6. cold trap; 7. a gas collection box; 8. an air pump; 9. a gas chromatograph; 10. a computer; 11. a nanosecond pulse power supply; 12. an oscilloscope; 13. a thermal infrared imager; 14. a water pump; 15. a heater; 16. an electromagnetic assembly; 17. a magnetic stirring plate; 18. an alternating current power supply; 19. a magnetic stirrer.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1:
as shown in fig. 1, embodiment 1 of the present disclosure provides an apparatus for plasma catalytic reforming of greenhouse gases, which includes four parts, namely a gas circuit, an electric circuit, a oil circuit and a reactor.
The gas circuit consists of an argon gas cylinder 1, a methane gas cylinder 3, a carbon dioxide gas cylinder 2, a mass flow meter, a one-way valve, a gas premixing groove, a soap film flow meter 5, a cold trap 6 and a gas collecting box 7.
In this embodiment, the argon gas cylinder 1 and the carbon dioxide gas cylinder 2 are respectively communicated with a first mass flow meter through a pipeline, the methane gas cylinder 3 is communicated with a second mass flow meter through a pipeline, the first mass flow meter and the second mass flow meter are respectively communicated with a gas premixing tank through a pipeline, and the gas premixing tank is communicated with a gas inlet at the top of the DBD reactor 4 through a pipeline.
The argon cylinder 1 is filled with high purity argon for reducing the catalyst in argon discharge plasma before the plasma catalytically reforms greenhouse gases.
The methane gas cylinder 3 is filled with high-purity methane gas, and the carbon dioxide gas cylinder 2 is filled with high-purity carbon dioxide gas. The mass flow meter is used for controlling the ratio of methane gas and carbon dioxide gas, and is beneficial to generating uniform and stable plasma. The one-way valve is used for controlling the one-way circulation of gas. The gas premixing groove is used for premixing methane and carbon dioxide gas in a certain proportion. The cold trap is used to prevent reverse reactions from occurring. The gas collecting box is used for collecting gas generated by the reaction.
The circuit part comprises a nanosecond pulse power supply 11, an alternating current power supply 18, an oscilloscope 12, an air pump 8, a gas chromatograph 9, a thermal infrared imager 13, a heater 15, a water pump 14, a computer 10 and a magnetic stirrer 19.
The bottom of the reactor is provided with a gas outlet which is communicated with a soap film flowmeter, a cold trap, a gas collecting box, a gas pump and a gas chromatograph in sequence through pipelines, and the chromatograph is connected with a computer terminal.
The nanosecond pulse power supply is used for providing an excitation source for the device, is connected with the inner electrode, and has the frequency of 0-15KHz, the output amplitude of 0-15kv, and the pulse rising time and the pulse falling time of 50-500 ns.
The oscilloscope is respectively connected with the input end of the DBD reactor and the output end of the DBD reactor through a high-voltage probe, induces the current of the output end of the DBD reactor through the Rogowski coil and is used for displaying the voltage waveform of the input end of the DBD reactor and the voltage and current waveform of the output end of the DBD reactor in real time;
the air pump is used for pumping out the collected products after reaction and analyzing gas components by using a gas chromatograph.
The thermal infrared imager is arranged on the outer side of the reactor, and a probe of the thermal infrared imager is over against a catalyst in the reactor and is used for collecting real-time temperature data of the DBD reactor.
The reactor outside is equipped with circulating oil, and the heater is used for heating circulating oil to provide stable temperature condition, and the water pump is used for making circulating oil reach the circulation state.
The alternating current power supply is connected with an electromagnetic assembly of the magnetic stirrer and used for providing power for the magnetic stirrer, and the magnetic stirrer is used for generating a magnetic field, changing the motion of charged particles in a discharge air gap and improving the collision reaction rate of electrons and methane carbon dioxide.
The reactor device used in this embodiment uses a coaxial cylindrical structure, including an inner cylinder with a smaller radius and an outer cylinder with a larger radius. The high-voltage inner electrode is not a traditional metal rod, but consists of a thorn-shaped aluminum rod and an aluminum foil tightly attached to the inner wall of the inner-layer quartz glass cylinder, and the thorn-shaped structure on the aluminum rod is tightly contacted with the aluminum foil. The electrode can obtain more high-energy electrons, enlarge the surface area of the electrode and enhance the reaction effect.
Meanwhile, the electrode structure has the arc-shaped outer surface of the traditional metal rod electrode, but the inside of the electrode structure is not completely solid, but is formed by closely contacting the thorn-shaped structure on the aluminum rod and the aluminum foil, the arrangement of the aluminum foil reduces the heat loss, and meanwhile, the heat generated by discharge can be diffused by utilizing the high heat conductivity of the aluminum rod on one hand, and can be diffused in time through the gaps among the thorn-shaped structures on the other hand, so that the inner glass cylinder is effectively prevented from being cracked due to the thermal expansion of the high-voltage inner electrode.
In this embodiment, the grounded outer electrode is covered by a stainless steel mesh, and both dielectric barrier layers are made of quartz material. Gas is introduced into the gap between the two quartz materials to discharge. The gas gap was filled with Ni-Al2O3 catalyst and fixed with quartz wool. An annular magnetic stirrer is sleeved at the bottom of the reactor, the magnetic field of the annular magnetic stirrer is fully utilized, the motion of charged particles in a discharge air gap is changed, the retention time of the charged particles in a discharge interval is increased, and the reaction of methane and carbon dioxide is promoted.
In this example, a magnetic stirrer was used under the catalyst, and as shown in fig. 2, the decomposition of methane and carbon dioxide was promoted by making full use of the magnetic field of the magnetic stirrer. A cylindrical cavity of the reactor is used as a stirring cavity for magnetic stirring, a central electrode of the reactor and a quartz medium layer wrapped on the central electrode are used as a fixed shaft, and a magnetic stirring plate vertical to the bottom surface of the stirring cavity is arranged around the fixed shaft. The outer side of the reactor is annularly arrayed with a plurality of electromagnetic components, and the polarity of the outer side of the magnetic stirring plate is the same as the polarity of the inner side of the electromagnetic components when the electromagnetic components are electrified, so that a magnetic field can be generated under the action of a magnetic stirrer externally connected with an alternating current power supply.
The excitation power supply, the supported metal catalyst and the DBD reactor of the packed bed DBD are optimized by combining a magnetic stirrer, so that the reasonable regulation and control of the gas conversion rate, the energy efficiency and the yield and the selectivity of high-value chemicals of the DBD plasma catalytic reforming greenhouse gas can be realized.
In the embodiment, the added magnetic field changes the motion of the charged particles in the discharge air gap, the charged particles change the original motion path under the action of the magnetic field, the retention time of the charged particles in a discharge interval is increased, in addition, the resistance of metal is increased due to the magneto-resistance effect, the conductive capacity is reduced, the energy loss of released high-energy electrons is reduced, and the collision reaction rate of the electrons and methane carbon dioxide is improved.
In the embodiment, the dielectric barrier discharge plasma is adopted to cooperate with the catalyst and the magnetic field, and the ionization, excitation, decomposition and other plasma reactions of the plasma on CH4 and CO2 are utilized to generate abundant charged particles, free radicals and excited-state particles, so that the collision reaction rate among the particles is increased, and the conversion of greenhouse gases is promoted.
Example 2:
the embodiment 2 of the present disclosure provides an operating method of an apparatus for plasma catalytic reforming of greenhouse gases, which utilizes the apparatus for plasma catalytic reforming of greenhouse gases described in the embodiment 1 of the present disclosure, and comprises the following steps:
the pulse power supply is switched on, and the electromagnetic assembly is electrified;
before the greenhouse gas is catalytically reformed by the plasma, introducing argon into a gap between a first cylinder and a second cylinder of the reactor, and reducing the catalyst in argon discharge plasma;
methane gas and carbon dioxide gas in a preset proportion are introduced into a gap between a first cylinder and a second cylinder of the reactor, and discharge is carried out under the action of an inner electrode;
the movement of the magnetic stirring plate generates a magnetic field, the original movement path of the charged particles is changed under the action of the magnetic field, and the retention time of the charged particles in a discharge interval is prolonged.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (10)
1. The device for catalytically reforming greenhouse gas by using the plasma is characterized by comprising a reactor, wherein the reactor comprises a first cylinder and a second cylinder which are coaxially nested, inner electrodes connected with a pulse power supply are arranged on the axes of the two cylinders, a grounding outer electrode is arranged on the outer side surface of the second cylinder, and a catalyst is filled in a gap between the first cylinder and the second cylinder;
the position that the lateral surface of first barrel is close to the reactor bottom surface is equipped with the magnetism stirring board that can follow the rotation of first barrel, and the lateral surface of second barrel is equipped with a plurality ofly and magnetism stirring board complex electromagnetic component, and the polarity that the one end of first barrel was kept away from to magnetism stirring board is the same with the circular telegram polarity that electromagnetic component is close to one side of second barrel.
2. The apparatus for plasma catalytic reforming of greenhouse gases as claimed in claim 1, wherein the inner electrode is an aluminum rod, and the surface of the aluminum rod is provided with a plurality of protrusions.
3. The apparatus for plasma catalytic reforming of greenhouse gases as claimed in claim 2, wherein the protrusions are each in contact with the aluminum foil of the inner surface of the first cylinder.
4. The apparatus for plasma catalytic reforming of greenhouse gases as claimed in claim 1, wherein a plurality of magnetic stirring plates having the same angle are fixed to the outer side surface of the first cylinder in the circumferential direction, and the movement space of the magnetic stirring plates is a gap between the first cylinder and the second cylinder;
or the magnetic stirring plate is vertical to the bottom surface of the reactor.
5. The apparatus for plasma catalytic reforming of greenhouse gases as claimed in claim 1, further comprising an argon storage device, a carbon dioxide storage device and a methane storage device, wherein the argon storage device and the carbon dioxide storage device are respectively communicated with the first mass flow meter through a pipeline, the methane storage device is communicated with the second mass flow meter through a pipeline, the first mass flow meter and the second mass flow meter are respectively communicated with the gas premixing tank through a pipeline, and the gas premixing tank is communicated with the gas inlet at the top of the reactor through a pipeline.
6. The apparatus for plasma catalytic reforming of greenhouse gases as claimed in claim 1, wherein the bottom of the reactor is provided with a gas outlet, the gas outlet is sequentially communicated with a soap film flowmeter, a cold trap, a gas collection tank, a gas pump and a gas chromatograph through pipelines, and the chromatograph is connected with a computer terminal.
7. The apparatus for plasma catalytic reforming of greenhouse gases of claim 6, further comprising an oscilloscope, an air pump, a thermal infrared imager, a water pump, and an ac power supply; the infrared thermal imager is used for acquiring real-time temperature data of the reactor and transmitting the real-time temperature data to the computer terminal; the heater is used for heating the circulating oil outside the reactor, the water pump is used for enabling the circulating oil to reach a circulating state, and the alternating current power supply is used for providing power for the magnetic stirrer.
8. The apparatus according to claim 1, wherein the grounded outer electrode is a stainless steel mesh covering the outer surface of the second cylinder, and the stainless steel mesh is grounded through a capacitor.
9. The apparatus for plasma catalytic reforming of greenhouse gases of claim 1, wherein the catalyst is Ni-Al2O3Catalyst, and the Ni-Al2O3The catalyst is fixed by quartz cotton.
10. A method for operating an apparatus for plasma catalytic reforming of greenhouse gases, characterized in that with an apparatus for plasma catalytic reforming of greenhouse gases according to any of claims 1-9, the method comprises the following steps:
the pulse power supply is switched on, and the electromagnetic assembly is electrified;
before the greenhouse gas is catalytically reformed by the plasma, introducing argon into a gap between a first cylinder and a second cylinder of the reactor, and reducing the catalyst in argon discharge plasma;
methane gas and carbon dioxide gas in a preset proportion are introduced into a gap between a first cylinder and a second cylinder of the reactor, and discharge is carried out under the action of an inner electrode;
the movement of the magnetic stirring plate generates a magnetic field, the original movement path of the charged particles is changed under the action of the magnetic field, and the retention time of the charged particles in a discharge interval is prolonged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010402738.6A CN111569803B (en) | 2020-05-13 | 2020-05-13 | A device and method for plasma catalytic reforming of greenhouse gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010402738.6A CN111569803B (en) | 2020-05-13 | 2020-05-13 | A device and method for plasma catalytic reforming of greenhouse gases |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111569803A CN111569803A (en) | 2020-08-25 |
| CN111569803B true CN111569803B (en) | 2021-10-19 |
Family
ID=72115471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010402738.6A Expired - Fee Related CN111569803B (en) | 2020-05-13 | 2020-05-13 | A device and method for plasma catalytic reforming of greenhouse gases |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111569803B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522020A (en) * | 2021-08-25 | 2021-10-22 | 江南大学 | A DBD plasma processing system for heterogeneous catalysis of normal atmospheric temperature |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09283449A (en) * | 1996-04-15 | 1997-10-31 | Mitsubishi Heavy Ind Ltd | Plasma chemical vapor deposition system |
| JPH11156185A (en) * | 1997-11-28 | 1999-06-15 | Fujitsu Ltd | Gas reactor |
| US7128816B2 (en) * | 2000-06-14 | 2006-10-31 | Wisconsin Alumni Research Foundation | Method and apparatus for producing colloidal nanoparticles in a dense medium plasma |
| CN103848484B (en) * | 2014-03-07 | 2016-08-31 | 南京大学 | A kind of device and method of low-temperature plasma synergistic bismuth molybdate catalysts degraded antibiotic waste water |
| JP6284825B2 (en) * | 2014-05-19 | 2018-02-28 | 東京エレクトロン株式会社 | Plasma processing equipment |
| JP6215171B2 (en) * | 2014-10-01 | 2017-10-18 | 東芝三菱電機産業システム株式会社 | Fine particle generator |
| JP6724837B2 (en) * | 2017-03-24 | 2020-07-15 | トヨタ自動車株式会社 | Plasma processing device |
| CN107592722B (en) * | 2017-08-25 | 2024-03-08 | 徐州燃烧控制研究院有限公司 | Magnetic rotating arc plasma generator |
-
2020
- 2020-05-13 CN CN202010402738.6A patent/CN111569803B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN111569803A (en) | 2020-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Recent developments in dielectric barrier discharge plasma-assisted catalytic dry reforming of methane over Ni-based catalysts | |
| Zhang et al. | A study on CO2 and CH4 conversion to synthesis gas and higher hydrocarbons by the combination of catalysts and dielectric-barrier discharges | |
| Liu et al. | Steam reforming of toluene as model biomass tar to H2-rich syngas in a DBD plasma-catalytic system | |
| Li et al. | Warm plasma catalytic reforming of biogas in a heat-insulated reactor: Dramatic energy efficiency and catalyst auto-reduction | |
| Duan et al. | Effect of dielectric packing materials on the decomposition of carbon dioxide using DBD microplasma reactor | |
| Zhu et al. | Plasma-catalytic synthesis of ammonia over Ru-based catalysts: Insights into the support effect | |
| Sun et al. | Large capacity hydrogen production by microwave discharge plasma in liquid fuels ethanol | |
| Ullah et al. | Recent trends in plasma-assisted CO2 methanation: a critical review of recent studies | |
| CN102500303B (en) | Device and method for converting mixed alcohol | |
| Lu et al. | Dielectric barrier discharge plasma assisted CO2 conversion: understanding the effects of reactor design and operating parameters | |
| CN103601150B (en) | Tube-tube type plasma reactor for preparing hydrogen through ammonia decomposition | |
| Meng et al. | Plasma‐driven CO2 hydrogenation to CH3OH over Fe2O3/γ‐Al2O3 catalyst | |
| Moshrefi et al. | Hydrogen production from methane decomposition in cold plasma reactor with rotating electrodes | |
| Bogaerts et al. | Plasma-based CO2 conversion | |
| Wu et al. | Synergistic effect of catalyst and plasma on CO2 decomposition in a dielectric barrier discharge plasma reactor | |
| CN102424646A (en) | Ethanol conversion method | |
| Jahanbakhsh et al. | Low-temperature CO2 splitting in a noncatalytic dielectric-barrier discharge plasma: effect of operational parameters with a new strategy of experimentation | |
| Yao et al. | Plasma-catalytic conversion of CO2 and H2O into H2, CO, and traces of CH4 over NiO/cordierite catalysts | |
| Ikeda et al. | Enhancing CO2 reduction: Insights from In-liquid microwave plasma chemical vapor deposition | |
| Xia et al. | CeO2-enhanced CO2 decomposition via frosted dielectric barrier discharge plasma | |
| Hatami et al. | CO2 conversion in a dielectric barrier discharge plasma by argon dilution over MgO/HKUST-1 catalyst using response surface methodology | |
| Xu et al. | Spark Discharge Plasma-Enabled CO2 Conversion Sustained by a Compact, Energy-Efficient, and Low-Cost Power Supply | |
| CN111569803B (en) | A device and method for plasma catalytic reforming of greenhouse gases | |
| Wang et al. | Stainless steel membrane distributor‐type dielectric barrier discharge plasma reactor for co‐conversion of CH4/CO2 | |
| Li et al. | Research Progress in DBD Plasma-Catalyzed CO2 Conversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211019 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |