CN111547681B - Method and device for preparing synthesis gas by dry reforming of methane under catalysis of plasma - Google Patents
Method and device for preparing synthesis gas by dry reforming of methane under catalysis of plasma Download PDFInfo
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- CN111547681B CN111547681B CN202010538772.6A CN202010538772A CN111547681B CN 111547681 B CN111547681 B CN 111547681B CN 202010538772 A CN202010538772 A CN 202010538772A CN 111547681 B CN111547681 B CN 111547681B
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Abstract
The invention discloses a method and a device for preparing synthesis gas by dry reforming methane under the catalysis of plasma, belonging to the technical field of methane and carbon dioxide reforming. The method comprises the following steps: the carbon dioxide and methane react under the coupling action of low-temperature plasma and a catalyst to generate synthesis gas mainly comprising carbon monoxide and hydrogen. The process can carry out the reforming of methane and carbon dioxide at lower reaction temperature and lower reaction pressure, thereby reducing the energy consumption of the device; the reaction unit is heated by the heating furnace, so that the reaction depth and the conversion rate of raw materials are easier to control, a large amount of carbon deposition cannot be generated, and the service life of the catalyst is prolonged. The device comprises a raw material gas distribution unit and a reaction unit, wherein a gas outlet of the raw material gas distribution unit is connected with a gas inlet of the reaction unit, an ionization cavity is formed between two electrodes in the reaction unit, an insulating medium is arranged in the ionization cavity, the heating furnace is surrounded on the outer side of a grounding electrode, and the two electrodes are electrically connected with a low-temperature plasma power supply.
Description
Technical Field
The invention relates to the technical field of methane and carbon dioxide reforming, in particular to a method and a device for preparing synthesis gas by dry reforming methane under the catalysis of plasma.
Background
Methane and carbon dioxide are typical greenhouse gases, and the development of a technology for preparing synthesis gas by reforming methane and carbon dioxide (also called methane dry reforming) can reduce the emission of greenhouse gases, change waste into valuable and obtain chemical intermediate products with economic values, thereby having double meanings. The technology mainly adopts a catalytic reforming method at present, but the method needs to be carried out at high temperature and high pressure; the device is complex and the energy consumption is high; carbon deposition is easily generated, so that the catalyst is deactivated and a pipeline is blocked.
In view of this, the invention is particularly proposed.
Disclosure of Invention
One of the objectives of the present invention includes providing a method for preparing synthesis gas by dry reforming methane under plasma catalysis, which can reform methane and carbon dioxide at a lower reaction temperature and a lower reaction pressure, reduce energy consumption, control reaction depth and conversion rate of raw materials, and avoid generating a large amount of carbon deposition, thereby prolonging the service life of the catalyst. In addition, the presence of the catalyst improves the selectivity of the low temperature plasma reforming reaction products.
The second purpose of the invention is to provide a device for preparing synthesis gas by dry reforming of methane under the catalysis of plasma, which has simple structure, low energy consumption, difficult generation of a large amount of carbon deposition and prolonged service life of the catalyst.
The application is realized as follows:
in a first aspect, the present application provides a method for producing synthesis gas by plasma-catalyzed dry reforming of methane, comprising the steps of:
the carbon dioxide and methane react under the coupling action of low-temperature plasma and a catalyst to generate synthesis gas mainly comprising carbon monoxide and hydrogen.
In an alternative embodiment, analysis of the syngas composition data is also included.
In an alternative embodiment, the reaction temperature is from 20 to 400 ℃, the absolute reaction pressure is from 100 to 200kPa, and the reaction residence time is from 0.1 to 10 s.
In alternative embodiments, the molar ratio of carbon dioxide to methane is from 0.1 to 10: 1.
In an alternative embodiment, the source of carbon dioxide and methane comprises at least one of a petrochemical produced gas, a coal chemical produced gas, and natural gas.
In alternative embodiments, the catalyst is a metal-loaded active support or a metal-loaded molecular sieve.
In an alternative embodiment, the catalyst has a particle size of 1 to 5 mm.
In an alternative embodiment, the supported metal comprises at least one of silver, nickel, zinc, and copper.
In an alternative embodiment, the active support comprises at least one of alumina and silica.
In alternative embodiments, the molecular sieve comprises ZSM-5 or HZSM-5.
In an alternative embodiment, the weight of the metal is from 0.5 to 20% of the weight of the catalyst.
In an alternative embodiment, the material of the high voltage electrode is a metallic material.
In an alternative embodiment, the material of the hv electrode comprises stainless steel or copper.
In an alternative embodiment, the material of the ground electrode is a metallic material.
In alternative embodiments, the material of the ground electrode comprises stainless steel or copper.
In alternative embodiments, the insulating medium comprises ceramic, glass, or quartz.
In a second aspect, the application provides a device for preparing synthesis gas by dry reforming of methane through plasma catalysis, which comprises a raw material gas distribution unit for distributing carbon dioxide and methane and a reaction unit for coupling reaction of carbon dioxide, methane, low-temperature plasma and a catalyst.
The gas outlet of the raw material gas distribution unit is connected with the gas inlet of the reaction unit.
The reaction unit comprises a low-temperature plasma reactor and a heating furnace, the low-temperature plasma reactor comprises a high-voltage electrode, a grounding electrode and an insulating medium, an ionization cavity which is communicated with the air outlet of the air distribution unit is formed between the high-voltage electrode and the grounding electrode, the insulating medium is arranged in the ionization cavity, a catalyst is filled in the ionization cavity, the heating furnace surrounds the outer side of the low-temperature plasma reactor, and the high-voltage electrode and the grounding electrode are electrically connected with two electrodes of a low-temperature plasma power supply.
In an alternative embodiment, the ionization chamber is filled with an amount of catalyst ranging from 5 to 50 g.
In an alternative embodiment, the plasma-catalyzed methane dry reforming synthesis gas production device further comprises a sample analysis unit, and the sample analysis unit is connected with the gas outlet of the reaction unit.
In alternative embodiments, the sample analysis unit comprises gas chromatography, mass spectrometry or gas chromatography-mass spectrometry.
In an alternative embodiment, the discharge spacing of the gas in the reaction cell is 1-10 mm.
In an alternative embodiment, the input power of the low-temperature plasma power supply is 20-500W, the input voltage is 0.5-265V, and the input current is 0.1-2.5A.
In an alternative embodiment, the high voltage electrode and the ground electrode cooperate in a plate-plate electrode configuration or a needle-cylinder electrode configuration.
In an alternative embodiment, the low temperature plasma is generated by a dielectric barrier discharge.
In an alternative embodiment, the material of the high voltage electrode is a metallic material.
In an alternative embodiment, the material of the hv electrode comprises stainless steel or copper.
In an alternative embodiment, the material of the ground electrode is a metallic material.
In alternative embodiments, the material of the ground electrode comprises stainless steel or copper.
In alternative embodiments, the insulating medium comprises ceramic, glass, or quartz.
The beneficial effects of the invention include:
according to the method for preparing the synthesis gas by the dry reforming of the methane under the catalysis of the plasma, the methane and the carbon dioxide are reformed through the low-temperature plasma, so that the whole reforming process can be carried out at a lower reaction temperature and reaction pressure, and the energy consumption of the device is reduced. The corresponding device for preparing the synthesis gas by catalyzing methane dry reforming with the plasma has a simple structure, and the selectivity of the low-temperature plasma reforming reaction product can be improved by generating the catalyst in the ionization cavity through the cooperation of the low-temperature plasma power supply and the reaction unit. And the heating furnace is arranged to supplement heat to the low-temperature plasma reactor, so that the reaction depth and the conversion rate of raw materials are easier to control, a large amount of carbon deposition cannot be generated, and the service life of the catalyst is prolonged. The device is adopted to carry out plasma catalytic methane dry reforming to prepare the synthesis gas, so that the problems that the existing catalytic reforming method needs to be carried out at high temperature and high pressure and carbon deposition is easily generated to cause catalyst inactivation and the like can be effectively solved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a plasma-catalyzed methane dry reforming syngas production plant provided herein;
fig. 2 is a schematic structural diagram of a reaction unit in a device for producing synthesis gas by plasma catalytic methane dry reforming provided by the present application.
Icon: 1-carbon dioxide; 2-methane; 3-raw material gas distribution unit; 4-a reaction unit; 41-high voltage electrode; 42-an insulating medium; 43-ground electrode; 44-heating furnace; 45-wire; 5-low temperature plasma power supply; 6-synthesis gas; 7-sample analysis unit.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The method and apparatus for producing synthesis gas by dry reforming methane through plasma catalysis are specifically described below.
The fourth state of the plasma as a substance is a conductive gas which is completely or partially ionized under the action of external energy, and the conductive gas comprises positive and negative ions, electrons, free radicals and active groups, and can collide with substance molecules at low temperature to initiate chemical reaction.
The inventor researches and discovers that the current catalytic reforming method generally uses thermal plasma to carry out dry reforming reaction of methane, and the method can obtain higher conversion rate of methane and carbon dioxide, but has lower selectivity of target products; and since the reactants are overheated, not only energy efficiency is low, but also a large amount of carbon deposition causes the reaction to be forcibly terminated after a period of time.
In view of the above, the present application provides a method for producing synthesis gas by dry reforming methane through plasma catalysis, comprising the following steps: the carbon dioxide and methane react under the coupling action of low-temperature plasma and a catalyst to generate synthesis gas mainly comprising carbon monoxide and hydrogen. Further, the method also comprises analyzing the composition data of the synthesis gas.
Correspondingly, the following plasma catalytic methane dry reforming synthesis gas apparatus, which includes a raw material gas distribution unit 3, a reaction unit 4 and a low-temperature plasma power supply 5, can be used to perform the above operations, referring to fig. 1.
The raw material gas distribution unit 3 is used for mixing the carbon dioxide 1 and the methane 2 according to a certain proportion, and preferably, the proportion of the carbon dioxide 1 and the methane 2 can be reasonably controlled and adjusted according to needs.
The gas outlet of the raw material gas distribution unit 3 is connected with the gas inlet of the reaction unit 4 so that the mixed carbon dioxide 1 and methane 2 are introduced into the reaction unit 4 and react under the coupling action of the catalyst and the low-temperature plasma to generate the synthesis gas 6 taking carbon monoxide and hydrogen as main components.
The feed gas distribution unit 3 may be provided with a carbon dioxide inlet and a methane inlet, and the inlets for the two gases may be separately provided or may be combined into one.
Referring to fig. 2, the reaction unit 4 includes a low temperature plasma reactor and a heating furnace 44, the low temperature plasma reactor includes a high voltage electrode 41, a ground electrode 43 and an insulating medium 42, an ionization chamber for communicating with an air outlet of the gas distribution unit is formed between the high voltage electrode 41 and the ground electrode 43, the ionization chamber is filled with carbon dioxide 1 and methane 2 mixed in the raw material gas distribution unit 3, and a catalyst is filled in the ionization chamber. The insulating medium 42 is disposed in the ionization chamber, two electrodes of the low-temperature plasma power supply 5 are electrically connected to the high-voltage electrode 41 and the grounding electrode 43 through the conducting wire 45, respectively, and when a sufficiently high voltage is applied between the high-voltage electrode 41 and the grounding electrode 43, the gas between the electrodes (in the ionization chamber) is broken down to generate dielectric barrier discharge to generate low-temperature plasma. The heating furnace 44 surrounds the outside of the low-temperature plasma reactor to supplement heat thereto.
The low-temperature plasma adopted in the method can control the reaction depth and the conversion rate of the raw materials more easily than the conventional thermal plasma, and a large amount of carbon deposition can not be generated, so that the service life of the catalyst is prolonged.
It should be noted that other structures of the low temperature plasma reactor can refer to the related art of the plasma reactor in the prior art, and will not be described herein in detail.
In an alternative embodiment, the apparatus for preparing synthesis gas by plasma-catalyzed dry reforming of methane further comprises a sample analysis unit 7, wherein the sample analysis unit 7 is connected with the gas outlet of the reaction unit 4, that is, the composition data of the synthesis gas 6 in the reaction unit 4 is analyzed by the sample analysis unit 7, so as to adjust the mixing ratio of the raw gas in the raw gas distribution unit 3 according to the guidance of the analysis result.
In alternative embodiments, the sample analysis unit 7 may comprise, for example, gas chromatography, mass spectrometry or gas chromatography-mass spectrometry.
Bearing, the plasma catalysis methane dry reforming system synthetic gas device that this application provided simple structure produces low temperature plasma through low temperature plasma power 5 and the cooperation of reaction unit 4 in order to reform carbon dioxide 1 and methane 2, can make whole reforming process go on under lower reaction temperature and reaction pressure to reduce the device energy consumption. The catalyst in the ionization chamber can improve the selectivity of the low-temperature plasma reforming reaction products. In addition, the heating furnace 44 is arranged to supplement heat to the low-temperature plasma reactor, so that the reaction depth and the conversion rate of raw materials are easier to control, a large amount of carbon deposition is avoided, and the service life of the catalyst is prolonged.
In a specific using process, the device for preparing the synthesis gas by dry reforming of the methane through plasma catalysis is adopted, carbon dioxide 1 and methane 2 in the gas distribution unit are conveyed to the reaction unit 4, the reaction unit 4 and the low-temperature plasma power supply 5 are switched on, so that gas in the reaction unit 4 reacts, and the synthesis gas 6 with carbon monoxide and hydrogen as main components is generated.
When the synthesis gas production device by plasma catalytic methane dry reforming further comprises a sample analysis unit 7, the synthesis gas 6 in the reaction unit 4 is introduced into the sample analysis unit 7 to detect the composition data of the synthesis gas 6.
In alternative embodiments, the reaction temperature within the reaction unit 4 may be set to 20 to 400 ℃ (e.g., 20 ℃, 80 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, or 400 ℃, etc.), the absolute reaction pressure may be set to 100-. The reaction temperature and pressure are both low, and the energy consumption can be effectively reduced.
In alternative embodiments, the discharge spacing of the gas within the reaction cell 4 may be set to 1-10mm, such as 2mm, 6mm or 10 mm. The smaller the discharge distance is, the smaller the thickness of the gas dielectric layer is, the easier the gas is to break down and discharge, and the better the discharge effect is. However, if the discharge gap is too small, for example, less than 1mm, the gas throughput tends to be too small.
In alternative embodiments, the input power of the low temperature plasma power supply 5 may be set to 20-500W (e.g., 20W, 100W, 200W, 300W, 400W, 500W, etc.), the input voltage may be set to 0.5-265V (e.g., 0.5V, 10V, 50V, 100V, 200V, 265V, etc.), and the input current may be set to 0.1-2.5A (e.g., 0.1A, 1A, 1.5A, 2A, 2.5A, etc.).
In alternative embodiments, the molar ratio of carbon dioxide 1 to methane 2 in the gas distribution unit may be, but is not limited to, 0.1 to 10:1, such as 0.1:1, 1:1, 5:1, 8:1, or 10:1, etc.
In alternative embodiments, the sources of carbon dioxide 1 and methane 2 are wide ranging, for example, the sources may include at least one of petrochemical produced gas, coal chemical produced gas, and natural gas.
In an alternative embodiment, the gas in the reaction unit 4 is reacted under the coupling action of the plasma and a catalyst, preferably a metal-loaded active support or a metal-loaded molecular sieve.
Wherein, the low-temperature plasma is generated by dielectric barrier discharge, and the high-voltage electrode 41 and the grounding electrode 43 are matched into a plate-plate electrode structure or a needle-cylinder electrode structure.
In alternative embodiments, the catalyst may have a particle size of 1 to 5mm, such as 1mm, 2mm, 3mm, 4mm, or 5mm, and the like.
In alternative embodiments, the supported metal may include, for example, at least one of silver, nickel, zinc, and copper. The active carrier may, for example, comprise at least one of alumina and silica.
In alternative embodiments, the molecular sieve comprises ZSM-5 or HZSM-5.
In alternative embodiments, the weight of the metal may be 0.5-20% of the weight of the catalyst, such as 0.5%, 1%, 5%, 10%, 15%, 20%, or the like.
In an alternative embodiment, the material of the high voltage electrode 41 may be a metallic material, such as stainless steel or copper. The material of the ground electrode 43 may also be a metallic material, such as stainless steel or copper. The insulating medium 42 may comprise, for example, ceramic, glass, quartz, or the like.
In the method, the synthesis gas is prepared by performing the plasma catalytic methane dry reforming, so that the problems that the existing catalytic reforming method needs to be performed at high temperature and high pressure and carbon deposition is easy to generate to cause catalyst inactivation and the like can be effectively solved.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1:
the reaction pressure is 140kPa (absolute pressure), the flow rate of carbon dioxide 1 is 0.5L/min, the flow rate of methane 2 is 1.5L/min, the mixture enters an ionization cavity of a low-temperature plasma reactor, alumina pellets (loaded with metal silver by 2.5 wt%) with the diameter of 3mm are filled in the low-temperature plasma reactor, the temperature of a heating furnace 44 at the outer side of the low-temperature plasma reactor is kept at 260 ℃, and a low-temperature plasma power supply 5 is switched on for dielectric barrier discharge. The low-temperature plasma reactor adopts a needle-cylinder type electrode structure, a cylindrical barrier medium is made of ceramics with the outer diameter of 25mm and the inner diameter of 20mm, the grounding electrode 43 is an annular stainless steel net, the high-voltage electrode 41 is a stainless steel rod with the diameter of 8mm, the electrode spacing (discharge spacing) is 6mm, and the effective discharge length of the low-temperature plasma reactor is 250 mm. The input voltage of the power supply is 220V, the input current is 1.5A, the input power is 330W, the reaction temperature is 390 ℃, and the retention time is 2.0 s.
The reaction result is: the conversion rate of carbon dioxide 1 is 56.6%, the conversion rate of methane 2 is 60.2%, the selectivity of carbon monoxide is 65.5%, and the selectivity of hydrogen is 70.0%. After 48h of reaction, a small amount of carbon was deposited on the catalyst. The catalyst can maintain the reaction activity after regeneration.
Example 2:
the only difference from example 1 is that the discharge gap is 10 mm.
The reaction result is: the conversion rate of carbon dioxide is 10.6%, the conversion rate of methane is 9.8%, the selectivity of carbon monoxide is 15.5%, and the selectivity of hydrogen is 16.1%. After 48h of reaction, a small amount of carbon was deposited on the catalyst. The catalyst can maintain the reaction activity after regeneration.
Example 3:
the only difference from embodiment 1 is that the input power is 100W.
The reaction result is: the conversion rate of carbon dioxide is 22.1 percent, the conversion rate of methane is 20.7 percent, the selectivity of carbon monoxide is 31.2 percent, and the selectivity of hydrogen is 35.7 percent. After 48h of reaction, a small amount of carbon was deposited on the catalyst. The catalyst can maintain the reaction activity after regeneration.
Example 4:
the only difference from example 1 is a residence time of 0.5S.
The reaction result is: the conversion rate of carbon dioxide is 35.7%, the conversion rate of methane is 32.4%, the selectivity of carbon monoxide is 40.5%, and the selectivity of hydrogen is 55.9%. After 48h of reaction, a small amount of carbon was deposited on the catalyst. The catalyst can maintain the reaction activity after regeneration.
Comparative example 1:
the difference from example 1 is only that no heating furnace is provided for heat retention.
The reaction result is: the conversion rate of carbon dioxide is 47.9 percent, the conversion rate of methane is 50.4 percent, the selectivity of carbon monoxide is 57.9 percent, and the selectivity of hydrogen is 60.4 percent. After 24h of reaction, there was significant carbon deposition on the catalyst.
Comparative example 2
The only difference from embodiment 1 is that the input power is 10W.
The reaction result is: the conversion rate of carbon dioxide 1 is 3.1%, the conversion rate of methane 2 is 2.2%, the selectivity of carbon monoxide is 14.7%, and the selectivity of hydrogen is 21.5%. After 48h of reaction, a small amount of carbon was deposited on the catalyst. The catalyst can maintain the reaction activity after regeneration.
Comparative example 3
The only difference from example 1 is that the residence time is 0.05 s.
The reaction result is: the conversion of carbon dioxide 1 was 5.0%, the conversion of methane 2 was 4.1%, the selectivity to carbon monoxide was 24.3%, and the selectivity to hydrogen was 19.8%. After 48h of reaction, a small amount of carbon was deposited on the catalyst. The catalyst can maintain the reaction activity after regeneration.
The corresponding results for the above examples and comparative examples can be summarized in Table 1:
TABLE 1 results
Wherein the selectivity of the product is defined as:
SCO＝[CO]b/(([CO2]a-[CO2]b)+([CH4]a-[CH4]b))×100％
SH2＝1/2[H2]b/([CH4]a-[CH4]b)×100％
in the formula: [ CO ]2]aAnd [ CH4]aRepresents CO2And CH4The inlet concentration of (d);
[CO2]b、[CH4]b、[CO]b、[H2]brepresents CO2、CH4、CO、H2Outlet concentration of (d).
Therefore, the heating furnace 44 is arranged outside the low-temperature plasma reactor, so that the conversion rate of raw materials and the selectivity of reaction products can be effectively improved, and meanwhile, a large amount of carbon deposition can not be generated, and the service life of the catalyst can be prolonged.
To sum up, the plasma catalysis methane dry reforming system synthetic gas device that this application provided simple structure produces low temperature plasma through low temperature plasma power and reaction unit cooperation in order to reform methane and carbon dioxide, can make whole reforming process go on under lower reaction temperature and reaction pressure to reduce the device energy consumption. And the reactor heating furnace is arranged for heat compensation, so that the reaction depth and the conversion rate of raw materials are easier to control, a large amount of carbon deposition cannot be generated, and the service life of the catalyst is prolonged. The device is adopted to carry out plasma catalytic methane dry reforming to prepare the synthesis gas, so that the problems that the existing catalytic reforming method needs to be carried out at high temperature and high pressure and carbon deposition is easily generated to cause catalyst inactivation and the like can be effectively solved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (22)
1. A method for preparing synthesis gas by dry reforming methane under the catalysis of plasma is characterized by comprising the following steps:
reacting carbon dioxide and methane under the coupling action of low-temperature plasma and a catalyst to generate synthesis gas mainly comprising carbon monoxide and hydrogen, and analyzing the composition data of the synthesis gas, wherein the low-temperature plasma is generated by dielectric barrier discharge, the reaction temperature is 20-400 ℃, the absolute reaction pressure is 100-200kPa, and the reaction residence time is 0.1-10 s;
the device for preparing the synthesis gas by dry reforming the methane through the plasma catalysis, which is used by the method, comprises a raw material gas distribution unit for distributing the carbon dioxide and the methane and a reaction unit for coupling and reacting the carbon dioxide, the methane, the low-temperature plasma and the catalyst;
the gas outlet of the raw material gas distribution unit is connected with the gas inlet of the reaction unit;
the reaction unit comprises a low-temperature plasma reactor and a heating furnace, the low-temperature plasma reactor comprises a high-voltage electrode, a grounding electrode and an insulating medium, an ionization cavity which is communicated with an air outlet of the air distribution unit is formed between the high-voltage electrode and the grounding electrode, the insulating medium is arranged in the ionization cavity, the catalyst is filled in the ionization cavity, the heating furnace surrounds the outer side of the low-temperature plasma reactor, and the high-voltage electrode and the grounding electrode are electrically connected with two electrodes of a low-temperature plasma power supply.
2. The method of claim 1, wherein the molar ratio of carbon dioxide to methane is from 0.1 to 10: 1.
3. The method of claim 1, wherein the sources of carbon dioxide and methane comprise at least one of petrochemical produced gas, coal chemical produced gas, and natural gas.
4. The process of claim 1, wherein the catalyst is a metal-loaded active support or a metal-loaded molecular sieve.
5. The process according to claim 4, wherein the catalyst has a particle size of 1 to 5 mm.
6. The method of claim 4, wherein the supported metal comprises at least one of silver, nickel, zinc, and copper.
7. The method of claim 4, wherein the active support comprises at least one of alumina and silica.
8. The method of claim 4, wherein the molecular sieve comprises ZSM-5 or HZSM-5.
9. The process of claim 4 wherein the weight of the metal is from 0.5 to 20% of the weight of the catalyst.
10. A plasma-catalyzed methane dry reforming synthesis gas generation apparatus for use in the method of any one of claims 1 to 9, comprising a feed gas distribution unit for distributing said carbon dioxide and said methane, and a reaction unit for coupling reaction of said carbon dioxide, said methane, said low temperature plasma and said catalyst;
the gas outlet of the raw material gas distribution unit is connected with the gas inlet of the reaction unit;
the reaction unit comprises a low-temperature plasma reactor and a heating furnace, the low-temperature plasma reactor comprises a high-voltage electrode, a grounding electrode and an insulating medium, an ionization cavity which is communicated with an air outlet of the air distribution unit is formed between the high-voltage electrode and the grounding electrode, the insulating medium is arranged in the ionization cavity, the catalyst is filled in the ionization cavity, the heating furnace surrounds the outer side of the low-temperature plasma reactor, and the high-voltage electrode and the grounding electrode are electrically connected with two electrodes of a low-temperature plasma power supply.
11. The apparatus for producing synthesis gas by plasma catalyzed dry reforming of methane according to claim 10, wherein the ionization chamber is filled with the catalyst in an amount of 5-50 g.
12. The device for producing synthesis gas by plasma catalytic dry reforming of methane according to claim 10, further comprising a sample analysis unit for analyzing composition data of the synthesis gas, wherein the sample analysis unit is connected with the gas outlet of the reaction unit.
13. The plasma-catalyzed methane dry reforming synthesis gas generation apparatus of claim 12, wherein the sample analysis unit comprises gas chromatography, mass spectrometry, or gas chromatography-mass spectrometry.
14. The apparatus for producing synthesis gas by plasma catalytic methane dry reforming according to claim 10, wherein the discharge pitch of the gas in the reaction unit is 1-10 mm.
15. The apparatus for producing synthesis gas by plasma catalytic dry reforming of methane according to claim 10, wherein the input power of the low temperature plasma power supply is 20-500W, the input voltage is 0.5-265V, and the input current is 0.1-2.5A.
16. The apparatus of claim 10, wherein the high voltage electrode and the ground electrode cooperate in a plate-plate electrode configuration or a pin-and-cylinder electrode configuration.
17. The apparatus according to claim 16, wherein the low temperature plasma is generated by a dielectric barrier discharge.
18. The apparatus according to claim 10, wherein the high voltage electrode is made of a metallic material.
19. The plasma-catalyzed methane dry reforming synthesis gas plant of claim 18, wherein the material of the high voltage electrode comprises stainless steel or copper.
20. The device for producing synthesis gas by plasma catalytic dry reforming of methane according to claim 18, wherein the material of the ground electrode is a metallic material.
21. The plasma-catalyzed methane dry reforming synthesis gas apparatus of claim 18, wherein the material of the ground electrode comprises stainless steel or copper.
22. The plasma-catalyzed methane dry reforming synthesis gas plant of claim 18, wherein the insulating medium comprises ceramic, glass, or quartz.
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