CN109867261B - Methane-carbon dioxide plasma catalytic reforming device and catalytic reforming method - Google Patents
Methane-carbon dioxide plasma catalytic reforming device and catalytic reforming method Download PDFInfo
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Abstract
The present disclosure discloses a methane-carbon dioxide plasma catalytic reforming device and a catalytic reforming method, comprising: the microwave power supply, the microwave backflow preventing device, the conversion waveguide, the three-pin tuner and the annular waveguide are connected in sequence, a microwave resonant cavity is formed in the annular waveguide, and a catalyst is filled in the microwave resonant cavity; the atmospheric pressure plasma jet device comprises an inner electrode, an outer electrode and a quartz glass tube, wherein the outer electrode is cylindrical, the quartz glass tube is sleeved in the outer electrode, the inner electrode is columnar, and the inner electrode is arranged on the central axis of the outer electrode; the anode and the cathode of the alternating current power supply are respectively connected with the inner electrode and the outer electrode; the carbon dioxide source and the methane source are connected with the air inlet end of the atmospheric pressure plasma jet device; the air outlet end of the atmospheric pressure plasma jet device is communicated with the inlet of the microwave resonant cavity. Can effectively solve the problems of high reaction temperature, low energy conversion efficiency, serious carbon deposition and the like in the traditional methane-carbon dioxide catalytic reforming method.
Description
Technical Field
The disclosure relates to the technical field of methane-carbon dioxide reforming, in particular to a methane-carbon dioxide plasma catalytic reforming device and a catalytic reforming method.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The global demand and inefficient use of non-renewable energy sources such as petroleum, natural gas, etc. by the human society causes excessive emissions of greenhouse gases and rapid exhaustion of fossil fuels. Methane is the main component of natural gas, mine gas and biogas, and is also an important hydrocarbon raw material for preparing commercial fuels and fine chemical products. Carbon dioxide widely exists in air, biogas and oilfield associated gas, and plays an important role in natural ecological balance and operation in modern society through photosynthesis, fuel combustion, organic decomposition and other modes. It is well known that methane and carbon dioxide are two common greenhouse gases in the atmospheric environment, and the realization of synchronous recycling of methane and carbon dioxide is important to ensure the energy safety of fossil fuels and reduce the greenhouse effect caused by climate change.
The methane-carbon dioxide dry reforming (Dry Forming ofMethane and Carbon Dioxide) technology can synchronously process the mixed gas consisting of methane and carbon dioxide, reform the mixed gas into the synthesis gas of hydrogen and carbon monoxide, and has environmental protection significance in reducing the emission of greenhouse gases. And H in methane carbon dioxide dry reforming product 2 The molar ratio of the catalyst to CO is low, which is favorable for further synthesis and preparation of long-chain hydrocarbon and high-added-value oxygen-containing compounds. However, the inventors found that the direct conversion reaction of methane with carbon dioxide (CH 4 +CO 2 →2H 2 +2CO) is a highly endothermic chemical reaction (274 KJ/mol), which results in the disadvantages of high reaction temperature, low conversion rate of methane and carbon dioxide, serious carbon deposition and the like of the catalytic reforming technology based on the traditional catalytic method, and limits the large-scale industrial application of the catalytic reforming of methane and carbon dioxide.
Disclosure of Invention
In view of the technical problems in the prior art, an object of the present disclosure is to provide a methane-carbon dioxide plasma catalytic reforming device and a catalytic reforming method. The reforming device and the reforming method can effectively solve the problems of high reaction temperature, low conversion rate of methane and carbon dioxide, serious carbon deposition and the like in the traditional methane-carbon dioxide catalytic reforming method.
In order to solve the above technical problems, the technical scheme of the present disclosure is:
a methane-carbon dioxide plasma catalytic reformer comprising:
the microwave power supply, the microwave backflow preventing device, the conversion waveguide, the three-pin tuner and the annular waveguide are connected in sequence, a microwave resonant cavity is formed in the annular waveguide, and a catalyst is filled in the microwave resonant cavity;
the atmospheric pressure plasma jet device comprises an inner electrode, an outer electrode and a quartz glass tube, wherein the outer electrode is cylindrical, the quartz glass tube is sleeved in the outer electrode, the inner electrode is columnar, and the inner electrode is arranged on the central axis of the outer electrode;
the anode and the cathode of the alternating current power supply are respectively connected with the inner electrode and the outer electrode;
the carbon dioxide source and the methane source are connected with the air inlet end of the atmospheric pressure plasma jet device;
the air outlet end of the atmospheric pressure plasma jet device is communicated with the inlet of the microwave resonant cavity.
A methane-carbon dioxide plasma catalytic reforming process comprising the steps of:
discharging the mixed gas of methane and carbon dioxide in an atmospheric pressure plasma jet device to generate an atmospheric pressure methane-carbon dioxide plasma jet;
the generated atmospheric methane-carbon dioxide plasma jet enters the microwave resonant cavity, and the catalytic reforming of methane-carbon dioxide plasma is realized under the synergistic effect of microwave discharge and a catalyst.
The beneficial effects of the present disclosure are:
the method realizes the plasma catalytic reforming of the methane carbon dioxide mixed gas under the condition of low atmospheric pressure and low temperature through the synergistic effect of atmospheric pressure plasma jet, microwave discharge and a catalyst. Can effectively solve the defects of high reaction temperature, low conversion rate of methane and carbon dioxide, serious carbon deposition and the like of the traditional methane and carbon dioxide catalytic reforming device.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate and explain the exemplary embodiments of the disclosure and together with the description serve to explain the disclosure, and do not constitute an undue limitation on the disclosure.
FIG. 1 is a schematic diagram of a plasma catalytic reformer in accordance with one or more embodiments of the present disclosure;
fig. 2 is a cross-sectional view of an annular waveguide in one or more embodiments of the present disclosure.
Wherein, 1, a microwave power supply, 2, a circulator, 3, a water load, 4, a three-pin adapter, 5 and a rotaryThe device comprises a waveguide changing device, a waveguide 6, an atmospheric pressure plasma jet device, a 7, an alternating current power supply, a 8, a grounding electrode, a 9, an annular waveguide, a 10, a microwave resonant cavity, a 11, a gas analyzer, a 12, a computer, a 13, a singlechip, a 14, a flowmeter, a 15, a second pressure reducing valve, a 16 and a CH 4 Gas cylinder, 17, CO 2 Gas cylinder, 18, catalyst.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present 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 exemplary embodiments in accordance with the present disclosure. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
A methane-carbon dioxide plasma catalytic reformer comprising:
the microwave power supply 1, the microwave backflow preventing device, the three-pin tuner 4, the conversion waveguide 5 and the annular waveguide 9 are connected in sequence, a microwave resonant cavity 10 is formed in the annular waveguide 9, and a catalyst 18 is filled in the microwave resonant cavity;
the atmospheric pressure plasma jet device comprises an inner electrode, an outer electrode and a quartz glass tube, wherein the outer electrode is cylindrical, the quartz glass tube is sleeved in the outer electrode, the inner electrode is columnar, and the inner electrode is arranged on the central axis of the outer electrode;
the positive electrode and the negative electrode of the alternating current power supply 7 are respectively connected with the inner electrode and the outer electrode;
the carbon dioxide source and the methane source are connected with the air inlet end of the atmospheric pressure plasma jet device;
the air outlet end of the atmospheric pressure plasma jet device is communicated with the inlet of the microwave resonant cavity.
The microwave power supply and the microwave power generator form a microwave power generation and control system which provides electric energy for the magnetron circuit of the microwave head.
A waveguide is a structure for directing electromagnetic waves.
The three-pin tuner is based on the principle of a stub tuning method, and the matching of load admittances is realized in a larger range. The method can be applied to various industrial microwave heating equipment and microwave plasma equipment to carry out impedance matching on a microwave transmission system.
The microwave backflow preventing device is used for isolating reflected waves and avoiding the reflected waves from damaging a microwave power supply;
the transition waveguide functions to propagate TE within the rectangular waveguide 10 Conversion of waves into TE propagating in annular waveguides 11 A wave;
the three-pin adjuster is characterized in that three pins capable of sliding up and down are inserted into the side wall of the rectangular waveguide, so that the problem of rapid matching of dynamic loads can be solved.
The discharge plasma can generate active components such as electrons, ions, free radicals, excited atoms, molecules and the like in various mixed gas atmospheres and wide air pressure ranges, and the non-equilibrium characteristic can overcome the thermodynamic barrier existing in the direct conversion reaction of methane and carbon dioxide in the traditional catalytic reforming technology. Therefore, the plasma catalytic reforming formed by combining the discharge plasma and the traditional catalytic reforming technology has wide market application prospect and important scientific research significance.
Under the atmospheric pressure condition, a relatively stable unbalanced discharge plasma is usually required to apply a strong electric field to a narrow discharge air gap, and an object to be treated can only be placed inside the discharge air gap, so that the structure and the size of the object to be treated are limited by the distance between the discharge air gaps, and the strong electric field is usually required to be formed under the excitation of an externally applied kV-level high-voltage power supply, so that the manufacturing cost of a device for the atmospheric pressure discharge plasma is high.
The atmospheric pressure plasma jet (Atmospheric Pressure Plasma Jet: APPJ) breaks through the limitation of traditional gas discharge, can realize the separation of the space of a discharge area and a working area, and can generate the atmospheric pressure unbalanced discharge plasma with low gas temperature and high chemical activity by a simple device structure. In addition, the APPJ can directly transport charged particles and active substances to the surface of an object to be treated and directly complete the treatment process, and has no special requirements on the external shape, geometric dimension and surface morphology of the object to be treated. The microwave discharge is a novel discharge plasma device for forming unbalanced discharge plasma in a microwave resonant cavity by using a waveguide or a transmission line to transmit microwave energy under the excitation of a microwave power supply. Compared with other forms of gas discharge, the microwave discharge has the advantages of uniformity, stability, high energy conversion efficiency, no electrode pollution, high density of charged particles and active particles and the like.
In the present disclosure, APPJ can not only achieve plasma reforming of methane carbon dioxide mixed gas, but also significantly improve seed electrons and other charged particle and active particle densities in the microwave discharge device, trigger and enhance microwave discharge. The microwave energy enters the annular waveguide through the microwave backflow prevention device, the three-pin adjuster and the conversion waveguide, and atmospheric methane carbon dioxide microwave discharge plasma is formed in the microwave resonant cavity. Through the synergistic effect of APPJ, microwave discharge and catalyst, the plasma catalytic reforming is realized under the condition of atmospheric pressure and low temperature.
In some embodiments, the microwave backflow prevention device comprises a circulator and a water load, wherein an inlet end and an outlet end of the circulator are respectively connected with a microwave power supply and a three-pin dispenser.
The microwave backflow preventing device is used for isolating reflected waves and preventing the reflected waves from damaging a microwave power supply.
The circulator is a device for enabling electromagnetic waves to be transmitted in a unidirectional annular mode, is a three-port device, the lower end of the circulator is connected with a water load through a flange, and the water load can adjust the water temperature through a cold water circulating pump.
The water load is a common high-power microwave matching load, and can be divided into an absorption type water load and a radiation type water load according to the working mode, and the water load is an absorber which utilizes flowing water as microwaves. The water load can play a role in backflow prevention and temperature reduction at the same time.
In some embodiments, the annular waveguide has a diameter of 15-25cm and an axial length of 13-17cm.
The diameter of the annular waveguide depends on the number of slits and large slits arranged on the inner wall of the annular waveguide, and six slits and one large slit are arranged in the reactor. According to the transmission theory of electromagnetic waves, when the slit position corresponds to the wave node of the microwaves in the annular waveguide, the microwave energy coupled into the quartz glass tube is maximum. Thus, the cavity dimensions should be determined according to the waveguide wavelength of the 2.45GHz microwave within the annular waveguide. TE is known from the related data 11 The wavelength is about 15.28cm and thus the diameter of the annular waveguide is about 19.46cm. The axial length need only be slightly greater than the length of the slit and the large slit.
In some embodiments, 6 slits and 1 large slit are arranged on the inner wall of the annular waveguide, the 6 slits are uniformly distributed in the circumferential direction of the annular waveguide in parallel with the axial direction of the annular waveguide, and the large slit is positioned opposite to the interface between the mode converter and the annular waveguide; the slits are uniformly distributed in the axial direction on the inner wall of the annular waveguide (except the area where the large slits are located).
Further, the length of the slit is 8-12cm, the width of the slit is 0.8-1.2cm, the length of the large slit is 8-12cm, and the width of the large slit is 4-6cm.
The ring waveguide forms a microwave resonant cavity inside. The circular output port of the transition waveguide enables microwave energy to be equally split into two paths of propagation within the annular waveguide. Under the combined action of the slit and the large slit in the annular waveguide and the constraint of the geometric dimension of the microwave resonant cavity, the microwave energy forms TE which is mainly under the action of the large slit in the microwave resonant cavity 11 And TM 01 Equal mode and slit-based TE 41 Etc. TE (TE) 11 And TM 01 The mode has the advantages of axisymmetry and central electric field strength, TE 41 The mode has the advantage of the field strength near the slit. The two modes realize complementary advantages, so that an electric field in the microwave resonant cavity is more uniform, and stable and dispersed atmospheric methane carbon dioxide microwave discharge plasma is formed in the microwave resonant cavity.
In some embodiments, the rectangular waveguide is a TE 10 Rectangular waveguide of mode.
In some embodiments, the diameter of the inner electrode in the atmospheric pressure plasma jet device is 2-4mm, the inner diameter of the outer electrode is 3-5cm, and the wall thickness of the quartz glass tube is 1.5-2.5mm.
The quartz glass tube is a dielectric layer for dielectric barrier discharge.
Further, the length of the inner electrode is 9-11cm, and the length of the outer electrode is 0.5-1mm.
In some embodiments, the end of the quartz glass tube is wrapped with a ground electrode.
In some embodiments, the catalytic reforming apparatus further comprises a gas analyzer in communication with the outlet of the microwave cavity. For analysing the gas composition after catalytic reforming.
In some embodiments, the carbon dioxide source is a carbon dioxide gas cylinder, the methane source is a methane gas cylinder, a first pressure reducing valve is arranged on an outlet pipeline of the carbon dioxide gas cylinder, and a first flowmeter is arranged at the downstream of the first pressure reducing valve;
and a second pressure reducing valve is arranged on an outlet pipeline of the methane gas cylinder, and a second flowmeter is arranged at the downstream of the second pressure reducing valve.
Further, the catalytic reforming device also comprises a computer and a singlechip, wherein the computer is respectively connected with the gas analyzer and the singlechip, and the singlechip is connected with the first flowmeter and the second flowmeter.
The gas analyzer can analyze the components in the gas after catalytic reforming, and if the components can not meet the requirements, the singlechip controls the opening of the first flowmeter and the second flowmeter so as to adjust the flow and the proportion of methane and carbon dioxide and improve the working efficiency of the methane-carbon dioxide plasma catalytic reforming device.
A methane-carbon dioxide plasma catalytic reforming process comprising the steps of:
discharging the mixed gas of methane and carbon dioxide in an atmospheric pressure plasma jet device to generate an atmospheric pressure methane-carbon dioxide plasma jet;
the generated atmospheric methane-carbon dioxide plasma jet enters the microwave resonant cavity, and the catalytic reforming of methane-carbon dioxide plasma is realized under the synergistic effect of microwave discharge and a catalyst.
In some embodiments, the power source to which the atmospheric pressure plasma jet device is connected is a 50Hz ac power source. For economy and convenience.
In some embodiments, the volume ratio of methane to carbon dioxide is 1-1.5:1.
In some embodiments, the flow rate of the mixed gas of methane and carbon dioxide is 50mL/min across the atmospheric pressure plasma jet device.
In some embodiments, the microwave power source is a 2.45GHz microwave power source.
In some embodiments, the catalyst is spherical Ni/CeO 2 /Al 2 O 3 A catalyst.
Further, ni-MgO/gamma-Al 2 O 3 The particle size of the catalyst is 3-5mm.
Further, the Ni-MgO/gamma-Al 2 O 3 The preparation method of the catalyst comprises the following steps: prepared using a step-wise impregnation method:
firstly, a certain amount of gamma-Al which is ground by a grinder is respectively weighed by an electronic day halving 2 O 3 The support was then coated with MgO (NO) at 2.5mol/L 3 ) 2 ·6H 2 Soaking in O solution for 24 hr, baking at 550deg.C for 1 hr, and cooling.
The cooled carriers were weighed in an amount of 3mol/LNi (NO 3 ) 2 ·6H 2 Soaking in O solution for 24 hr, roasting at 600deg.C for 6 hr, and introducing H under 650 2 Reducing for 2h to obtain Ni-MgO/gamma-Al 2 O 3 A catalyst.
In some embodiments, the temperature of the methane-carbon dioxide plasma catalytic reforming is 400-700K.
In the methane-carbon dioxide plasma catalytic reforming method, APPJ can realize the plasma reforming of methane-carbon dioxide mixed gas, and can also remarkably improve the density of seed electrons and other charged particles and active particles in a microwave discharge device, trigger and enhance microwave discharge.
Example 1
As shown in fig. 1 and 2, a methane-carbon dioxide plasma catalytic reforming apparatus includes:
the microwave power supply 1, the circulator 2, the water load 3, the three-pin tuner 4, the conversion waveguide 5 and the annular waveguide 9 are sequentially connected, a microwave resonant cavity is formed in the annular waveguide 9, and a catalyst 18 is filled in the microwave resonant cavity;
the atmospheric pressure plasma jet device 6 comprises an inner electrode, an outer electrode and a quartz glass tube, wherein the outer electrode is cylindrical, the quartz glass tube is sleeved in the outer electrode, the inner electrode is columnar, the inner electrode is arranged on the central axis of the outer electrode, and the end part of the quartz glass tube is wound with a grounding electrode 8;
the positive electrode and the negative electrode of the alternating current power supply 7 are respectively connected with the inner electrode and the outer electrode;
the carbon dioxide gas cylinder 17 is connected with the air inlet end of the atmospheric pressure plasma jet device 6 through a first pressure reducing valve and a first flowmeter, and the methane gas cylinder 16 is connected with the air inlet end of the atmospheric pressure plasma jet device 6 through a second pressure reducing valve 15 and a second flowmeter 14;
the air outlet end of the atmospheric pressure plasma jet device 6 is communicated with the inlet of the microwave resonant cavity; the outlet of the microwave resonant cavity is connected with a gas analyzer 11, the gas analyzer 11 is connected with a computer 12, the computer 12 is connected with a singlechip 13, and the singlechip 13 is connected with a first flowmeter and a second flowmeter.
Example 2
A methane-carbon dioxide plasma catalytic reforming process comprising the steps of:
discharging the mixed gas of methane and carbon dioxide in a volume ratio of 1.3:1 in an atmospheric pressure plasma jet device, wherein the discharge voltage is of KV magnitude, and generating an atmospheric pressure methane-carbon dioxide plasma jet;
the generated atmospheric methane-carbon dioxide plasma jet enters the microwave resonant cavity, and the catalytic reforming of methane-carbon dioxide plasma is realized under the synergistic effect of microwave discharge and a catalyst;
the microwave frequency is 2.45GHZ, and the catalytic reforming is carried outThe temperature is 480K; the catalyst is Ni-MgO/gamma-Al 2 O 3 And the particle size of the catalyst is 3-5mm. Within 1 hour of operation, no macroscopic carbon deposit was observed on the inner wall of the device.
The conversion of methane and carbon dioxide was 91% and 92%, respectively.
Example 3
A methane-carbon dioxide plasma catalytic reforming process comprising the steps of:
discharging the mixed gas of methane and carbon dioxide in a volume ratio of 1:1 in an atmospheric pressure plasma jet device, wherein the discharge voltage is KV level, and generating an atmospheric pressure methane-carbon dioxide plasma jet;
the generated atmospheric methane-carbon dioxide plasma jet enters the microwave resonant cavity, and the catalytic reforming of methane-carbon dioxide plasma is realized under the synergistic effect of microwave discharge and a catalyst;
the microwave frequency is 2.45GHZ, and the catalytic reforming temperature is 477K; the catalyst is Ni-MgO/gamma-Al 2 O 3 And the particle size of the catalyst is 3-5mm. Within 1 hour of operation, no macroscopic carbon deposit was observed on the inner wall of the device.
The conversion of methane and carbon dioxide was 89% and 94%, respectively.
Example 4
A methane-carbon dioxide plasma catalytic reforming process comprising the steps of:
discharging the mixed gas of methane and carbon dioxide in a volume ratio of 1.5:1 in an atmospheric pressure plasma jet device, wherein the discharge voltage is of KV magnitude, and generating an atmospheric pressure methane-carbon dioxide plasma jet;
the generated atmospheric methane-carbon dioxide plasma jet enters the microwave resonant cavity, and the catalytic reforming of methane-carbon dioxide plasma is realized under the synergistic effect of microwave discharge and a catalyst;
the microwave frequency is 2.45GHZ, and the catalytic reforming temperature is 482K; the catalyst is Ni-MgO/gamma-Al 2 O 3 And the particle size of the catalyst is 3-5mm. Within 1 hour of operation, no macroscopic product is on the inner wall of the deviceAnd (3) carbon.
The conversion of methane and carbon dioxide was 92% and 91%, respectively.
The foregoing description of the preferred embodiments of the present disclosure is provided only and not intended to limit the disclosure so that various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (10)
1. A methane-carbon dioxide plasma catalytic reforming device, characterized in that: comprising the following steps:
the microwave power supply, the microwave backflow preventing device, the conversion waveguide, the three-pin tuner and the annular waveguide are connected in sequence, a microwave resonant cavity is formed in the annular waveguide, and a catalyst is filled in the microwave resonant cavity;
the atmospheric pressure plasma jet device comprises an inner electrode, an outer electrode and a quartz glass tube, wherein the outer electrode is cylindrical, the quartz glass tube is sleeved in the outer electrode, the inner electrode is columnar, and the inner electrode is arranged on the central axis of the outer electrode;
the anode and the cathode of the alternating current power supply are respectively connected with the inner electrode and the outer electrode;
the carbon dioxide source and the methane source are connected with the air inlet end of the atmospheric pressure plasma jet device;
the air outlet end of the atmospheric pressure plasma jet device is communicated with the inlet of the microwave resonant cavity;
the catalytic reforming device also comprises a gas analyzer, wherein the gas analyzer is communicated with the outlet of the microwave resonant cavity and is used for analyzing the gas components after catalytic reforming;
the catalytic reforming device also comprises a computer and a singlechip, wherein the computer is respectively connected with the gas analyzer and the singlechip, and the singlechip is connected with the first flowmeter and the second flowmeter.
2. The catalytic reforming device of claim 1 wherein: the microwave backflow prevention device comprises a circulator and a water load, wherein the inlet end and the outlet end of the circulator are respectively connected with a microwave power supply and a three-pin adapter, the circulator is a three-port device, and the lower end of the circulator is connected with the water load through a flange.
3. The catalytic reforming device of claim 1 wherein: the diameter of the annular waveguide is 15-25cm, and the axial length is 13-17cm.
4. The catalytic reforming device of claim 1 wherein: the inner wall of the annular waveguide is provided with 6 slits and 1 large slit, the 6 slits are uniformly distributed in the circumferential direction of the annular waveguide in parallel with the axial direction of the annular waveguide, and the large slit is positioned opposite to the interface between the mode converter and the annular waveguide;
the length of the slit is 8-12cm, the width of the slit is 0.8-1.2cm, the length of the large slit is 8-12cm, and the width of the large slit is 4-6cm.
5. The catalytic reforming device of claim 1 wherein: the diameter of the inner electrode in the atmospheric pressure plasma jet device is 2-4mm, the inner diameter of the outer electrode is 3-5cm, and the wall thickness of the quartz glass tube is 1.5-2.5mm.
6. The catalytic reforming device of claim 1 wherein: the length of the inner electrode is 9-11cm, and the length of the outer electrode is 0.5-1mm.
7. A catalytic reforming process based on a methane-carbon dioxide plasma catalytic reforming apparatus according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
discharging the mixed gas of methane and carbon dioxide in an atmospheric pressure plasma jet device to generate an atmospheric pressure methane-carbon dioxide plasma jet;
the generated atmospheric methane-carbon dioxide plasma jet enters the microwave resonant cavity, and the catalytic reforming of methane-carbon dioxide plasma is realized under the synergistic effect of microwave discharge and a catalyst.
8. The catalytic reforming process of claim 7 wherein: the volume ratio of methane to carbon dioxide is 1-1.5:1.
9. The catalytic reforming process of claim 7 wherein: the catalyst is Ni-MgO/gamma-Al 2 O 3 A catalyst.
10. The catalytic reforming process of claim 7 wherein: the temperature of the methane-carbon dioxide plasma catalytic reforming is 400-700K.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007113570A (en) * | 2005-09-20 | 2007-05-10 | Imagineering Kk | Ignition device, internal combustion engine, ignition plug, plasma device, exhaust gas decomposition device, ozone generation/sterilization/infection device, and deodorizing device |
| CN102363521A (en) * | 2011-11-03 | 2012-02-29 | 吉林大学 | Vehicle-mounted microwave low-temperature plasma reformer system for online hydrogen production |
| CN104071747A (en) * | 2014-07-14 | 2014-10-01 | 大连理工大学 | Method for preparing synthesis gas through methane reforming with plasma |
| CN105122042A (en) * | 2013-03-13 | 2015-12-02 | 拉多姆公司 | Microwave plasma spectrometer using dielectric resonator |
| CN209872349U (en) * | 2019-02-28 | 2019-12-31 | 山东师范大学 | Methane-carbon dioxide plasma catalytic reforming device |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007113570A (en) * | 2005-09-20 | 2007-05-10 | Imagineering Kk | Ignition device, internal combustion engine, ignition plug, plasma device, exhaust gas decomposition device, ozone generation/sterilization/infection device, and deodorizing device |
| CN102363521A (en) * | 2011-11-03 | 2012-02-29 | 吉林大学 | Vehicle-mounted microwave low-temperature plasma reformer system for online hydrogen production |
| CN105122042A (en) * | 2013-03-13 | 2015-12-02 | 拉多姆公司 | Microwave plasma spectrometer using dielectric resonator |
| CN104071747A (en) * | 2014-07-14 | 2014-10-01 | 大连理工大学 | Method for preparing synthesis gas through methane reforming with plasma |
| CN209872349U (en) * | 2019-02-28 | 2019-12-31 | 山东师范大学 | Methane-carbon dioxide plasma catalytic reforming device |
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