CN112897463B - Device and method for preparing synthesis gas by electrocatalysis of methane-carbon dioxide - Google Patents
Device and method for preparing synthesis gas by electrocatalysis of methane-carbon dioxide Download PDFInfo
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Abstract
The invention relates to a device and a method for preparing synthesis gas by electrocatalysis of methane-carbon dioxide. The device comprises a reaction device, a catalyst packing area is arranged in the reaction device, electrode plates are respectively arranged on two sides of the catalyst packing area, and the electrode plates on the two sides are respectively connected with a positive electrode and a negative electrode; and the gas supply device is connected with the gas supply port of the reaction device, and the gas inlet of the reaction device is positioned outside the space formed by the electrode plates. The synthesis gas is prepared by electrocatalysis. The catalyst is placed in the filler area, the two sides of the catalyst are respectively provided with the electrode plates, an electric field is formed between the two electrode plates, and methane and carbon dioxide gas perform catalytic reaction under the action of the electric field, so that the catalyst has the advantages of low reaction temperature and high conversion rate.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a device and a method for preparing synthesis gas by electrocatalysis of methane-carbon dioxide.
Background
The information in this background section is only for enhancement of 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 that is already known to a person of ordinary skill in the art.
Since the industrial revolution, the demand of human beings for fossil energy has increased day by day, but the combustion of fossil energy emits a large amount of CO 2 Thereby causing the greenhouse effect to be intensified. Natural gas is a high-efficiency clean energy and also an important chemical raw material; its main component is CH 4 Therefore, the production and the life by reasonably utilizing the natural gas become hot topics gradually, and the natural gas market in China has great potential. However, compared with developed countries, the utilization of natural gas in China mainly stays in the traditional fields of urban gas, power generation, automobile fuel and the like by taking the natural gas as a raw material, and only about 15% of the natural gas is used in the chemical field. With the gradual progress of the global energy structureThe step adjustment is carried out at home and abroad, the chemical raw material route is adjusted, and the reasonable utilization of natural gas is the most important thing and is one of the research hotspots in the chemical field at present.
At present, the main application of methane in the chemical field is the reforming of synthesis gas, CH 4 There are three main ways of producing synthesis gas: (1) CH (CH) 4 Steam reforming; (2) CH (CH) 4 Partial oxidation reforming; (3) CH (CH) 4 -CO 2 And (4) reforming. The former two methods have the disadvantages of high energy consumption, unclear reaction mechanism, high operation cost and H 2 the/CO is higher (more than 3), which is not beneficial to Fischer-Tropsch synthesis and the like. CH (CH) 4 -CO 2 Reforming has the unique advantage of, CH 4 And CO 2 Both are greenhouse gases, CH 4 -CO 2 The reforming reaction can control the greenhouse effect to a certain extent on one hand, and is a new chemical raw material synthesis method on the other hand. In addition, the methane carbon dioxide reforming reaction also has natural advantages, natural gas contains carbon dioxide with certain concentration, the technology can directly use the natural gas without separating the natural gas, and the separation cost can be greatly saved, so that more and more scholars in recent years can carry out CH (CH) reforming reaction 4 -CO 2 Much effort has been devoted to reforming research.
CH 4 -CO 2 The reforming method mainly comprises conventional thermal catalytic reforming, plasma catalytic reforming and the like. The conventional thermocatalytic reforming method needs to be carried out at high temperature, has high energy consumption, and is not beneficial to industrialization because the catalyst is easy to be inactivated due to sintering and carbon deposition. Plasma catalyzed CH 4 -CO 2 The reforming technology has low energy efficiency, high equipment requirement, high cost, large operation difficulty and insufficient industrial operation.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide an apparatus and method for producing synthesis gas by electrocatalysis of methane-carbon dioxide.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, an apparatus for electrocatalytic production of synthesis gas from methane-carbon dioxide comprises,
the reaction device is internally provided with a catalyst packing area, two sides of the catalyst packing area are respectively provided with an electrode plate, and the electrode plates on the two sides are respectively connected with a positive electrode and a negative electrode;
and the gas supply device is connected with the gas supply port of the reaction device, and the gas inlet of the reaction device is positioned outside the space formed by the electrode plates.
The invention provides a device for preparing synthesis gas, which utilizes electrocatalysis to prepare the synthesis gas. The catalyst is placed in the filler region, the electrode plates are respectively arranged on two sides of the catalyst, and an electric field is formed between the two electrode plates, so that the catalyst is positioned in the region of the electric field. Under the action of an electric field, methane and carbon dioxide gas carry out catalytic reaction, and the method has the advantages of low reaction temperature and high conversion rate.
In some embodiments of the invention, the reaction apparatus is provided with an air outlet, the air outlet being disposed at an end opposite to the air inlet. Allowing the gases to react through the catalyst zone.
In some embodiments of the invention, the gas supply means comprises a reactant gas supply means and a carrier gas supply means, and the reactant gas supply means comprises a methane gas supply means and a carbon dioxide gas supply means. The carrier gas is generally inert gas, which improves the flow rate and mixing effect of the reaction gas.
In some embodiments of the present invention, the gas supply means further comprises a gas mixer, the gas mixer being connected to the reaction gas supply means and the carrier gas supply means, respectively.
In a second aspect, a method for preparing synthesis gas by electrocatalysis of methane-carbon dioxide comprises the following specific steps:
raising the temperature within the reaction apparatus;
introducing mixed gas of reaction gas and carrier gas into the reaction device;
the reaction gas is subjected to reforming reaction under the action of an electric field to obtain the synthesis gas.
It is possible to perform a catalytic reaction by plasma, but plasma is based on the interaction between positive and negative ions generated after ionization and a catalyst and a reaction gas. However, releasing the plasma requires a high voltage to promote the ionization process, which requires a large energy consumption.
The invention utilizes the action of an electric field to carry out catalytic reforming reaction. The electric field is present between the two electrode plates, which act on a different principle and are generated in a different way than plasma. And the energy consumption is low.
The electric field can lower the temperature of the reforming reaction and can excite the generation of thermal electrons, CH in the process 4 The cracking reaction and the disproportionation reaction of CO generate a large amount of cracking carbon which is attached to the surface of the catalyst to form carbon deposition, and the carbon deposition can play a transition role under the action of an electric field and hot electrons and participate in the reforming reaction to realize the cyclic transfer of carbon.
In some embodiments of the invention, the temperature of the reaction apparatus is from 350 to 500 ℃; further 400-500 ℃. The temperature of catalytic reforming is much lower than conventional thermocatalysis 700 ℃. The energy consumption is reduced. The process is easier to realize.
In some embodiments of the invention, the reaction apparatus is packed with a catalyst, the catalyst is a Fe, ni doped carbon based catalyst, and the catalyst is activated carbon loaded with iron oxide and nickel oxide. The nickel oxide and the iron oxide supported on the activated carbon make the activated carbon have more appropriate conductivity because the electric field is applied to the catalyst and the reformed gas, and the catalyst has appropriate conductivity, which affects the effect of the catalyst subjected to the electric field. If the conductivity is too low, the influence of an electric field on the catalyst is too small, and the catalytic reforming reaction is not favorably carried out.
Further, the mass of 1g of nickel oxide supported on the activated carbon is 0.005-0.025g, and the mass of 1g of iron oxide supported on the activated carbon is 0.025-0.045g; further, 1g of nickel oxide supported on the activated carbon was 0.01 to 0.02g in mass, and 1g of iron oxide supported on the activated carbon was 0.03 to 0.04g in mass.
In some embodiments of the invention, the current is direct current, and the current intensity is 2-10mA; further 3-9mA. As the current increases, the conversion of carbon dioxide and methane increases.
In some embodiments of the invention, the reaction apparatus has an inlet gas flow rate of 80 to 120ml/min; further 90-11ml/min.
In some embodiments of the present invention, a method for preparing a Fe, ni doped carbon-based catalyst comprises the following specific steps:
heating activated carbon in water, cleaning and drying;
putting the dried activated carbon into a suspension solution of Fe and Ni precursors;
and drying and calcining the impregnated and loaded activated carbon to obtain the Fe and Ni doped carbon-based catalyst.
In some embodiments of the invention, the number of activated carbon water washes is 3 to 15; further preferably 5 to 10 times; specifically, the number of the reaction is 6, 7, 8, 9 or 10; more preferably 8 times. The activated carbon is repeatedly washed by water for many times, so that the conductivity of the activated carbon is influenced. The nature and quantity of the activated carbon attached and the structure of the activated carbon itself are different at different washing times.
In some embodiments of the invention, the water temperature of the activated carbon water wash is 70-120 ℃; further 80-110 ℃. The temperature of the water affects the cleaning effect.
In some embodiments of the invention, the temperature for drying the activated carbon after washing is 100-130 ℃, and the drying time is 10-16h; further at 105-110 deg.c for 12-15 hr.
In some embodiments of the invention, the Fe, ni precursors in the suspension solution of Fe, ni precursors are nickel nitrate and iron nitrate, respectively; further Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O。
In some embodiments of the invention, the mass ratio of Fe, ni precursor to water in the suspension solution of Fe, ni precursor is 1:3-4; further 1.
In some embodiments of the invention, the mass ratio of activated carbon to the suspension of Fe, ni precursors is 1:1-2; further 1.5.
In some embodiments of the invention, the ultrasonic treatment is performed during the mixing process of the activated carbon and the suspension solution of the Fe and Ni precursors, and the ultrasonic treatment time is 1-4h; further 2-3h.
In some embodiments of the invention, the temperature of drying after impregnation loading is 100-130 ℃, and the time of drying is 10-16h; further at 105-110 deg.c for 12-15 hr.
In some embodiments of the invention, the temperature of calcination is 450-600 ℃ and the time of calcination is 3-6h; furthermore, the calcining temperature is 500-600 ℃, and the calcining time is 4-6h.
One or more technical schemes of the invention have the following beneficial effects:
(1) The invention prepares the synthesis gas by reforming the methane-carbon dioxide through electric field catalysis, and has the characteristics of high conversion rate and low reaction temperature. When the conventional thermal catalysis method is used for reforming to prepare the synthetic gas, the conversion rate is obvious when the temperature is required to be over 700 ℃, and when an electric field acts on a catalyst with proper conductivity, the generation of hot electrons can be excited, so that CH can be generated 4 -CO 2 The reforming reaction can have a good conversion at 400 ℃. The invention finds that when the electric field acts on the catalyst with proper conductivity, the reaction temperature can be effectively reduced, and the reaction efficiency is improved.
(2) The invention finds that the activated carbon has proper conductivity for electric field catalysis after being washed by water. And Fe and Ni metal oxides are loaded on the treated activated carbon carrier, compared with a noble metal catalyst, the catalyst has proper conductivity and low price, carbon deposition in the reaction process can play a role of transition carbon to participate in the reforming reaction, the cyclic transfer cycle of carbon is realized, and CH under an electric field can be realized 4 -CO 2 Reforming to prepare synthesis gas. Cheap catalytic materials such as iron, nickel, activated carbon and the like are widely applied, but the materials cannot be used in the field of electric field catalytic reforming of methane and carbon dioxide, the pretreated activated carbon not only has proper conductivity, but also can realize partial carbon circulation to reduce carbon deposition, and meanwhile, the loaded iron and nickel can excite hot electrons to strengthen the preparation of synthesis gas.
(3) The invention can effectively explore the performance of the catalyst for preparing hydrogen and carbon monoxide by combining the electric field generating device and the traditional heating equipment, thereby not only improving the catalytic efficiency and reducing the reaction temperature, but also reducing the experiment cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic diagram of an apparatus for producing synthesis gas based on electric field catalysis of methane-carbon dioxide in example 1 of the present invention.
Fig. 2 is a schematic diagram of an Fe and Ni doped carbon based catalyst in example 2 of the present invention.
FIG. 3 is a schematic diagram showing the change of conductivity of coconut shell granular activated carbon after water washing treatment in example 2 of the present invention
FIG. 4 is a graph showing CH when different current intensities at 400 ℃ are applied to reforming reaction in example 3 of the present invention 4 And CO 2 Schematic representation of conversion.
FIG. 5 is an electron microscope scanning image of the fresh catalyst and the catalyst at 9mA current intensity for 200min in example 3 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 invention 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 application. 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.
As described in the background, in evaluating CH 4 -CO 2 In the process of reforming the performance of the synthesis gas, the economic cost of independently using a traditional heating furnace as a heat source is too high, the temperature required by the thermodynamics of the reforming reaction is often over 700 ℃, the heating and temperature rising needs a long time, the long heating time leads to an experimental period of about 1.5-2h, and the phenomenon of carbon deposition and sintering deactivation easily occurs when the catalyst is kept at a high temperature for a long time, so that a plurality of problems exist in the aspects of the experimental period, the experimental cost, the energy efficiency and the like. Therefore, the invention provides an electric field-based catalytic CH 4 -CO 2 A device and a method for preparing synthesis gas by reforming, and a preparation method and application of a Fe and Ni doped carbon-based catalyst; the invention will now be further described with reference to the accompanying drawings and detailed description.
Example 1
An apparatus for electrocatalytic production of synthesis gas from methane-carbon dioxide, with reference to fig. 1, comprising: the gas mixer 7, the direct-current high-voltage power supply 8, the electrode 9, the thermocouple 10, the electrode plate 11, the reaction device 13 and the catalyst 12 are arranged in the reaction device 13. The electrode plates 11 are arranged above and below the catalyst 12; the thermocouple 10 is arranged in the middle of the catalyst 12 through an electrode plate 11; one end of the electrode 9 is connected with the electrode plate 11, and the other end is connected with the direct-current high-voltage power supply 8. The device also comprises a methane gas supply device 1, a carbon dioxide gas supply device 2 and a carrier gas supply device 3.
In this embodiment, the reaction apparatus 13 is a tube furnace, and the catalyst and the electrode plate are fixed inside the tube furnace by a support device.
In the present embodiment, a flow meter 4, a temperature measuring instrument 14, a chromatograph 15, a first three-way valve 5, and a second three-way valve 6 are further included.
The methane gas supply device 1 and the carbon dioxide gas supply device 2 are communicated with two ports of a first three-way valve 5, and a flow controller 4 is arranged on the section of pipeline; the other port of the first three-way valve 5 is connected with one port of a second three-way valve 6; the carrier gas supply device 3 is communicated with the other port of the second three-way valve 6, and the flow controller 4 is arranged on the section of pipeline; the last port of the second three-way valve 6 is connected with the inlet of a gas mixer 7; the outlet of the gas mixer 7 is communicated with the inlet of the reaction device 13 through a pipeline; the outlet of the reactor 16 is connected to a chromatograph 15 via a pipe.
Example 2
A method for preparing a Fe and Ni doped carbon-based catalyst, referring to fig. 2, comprising the following steps:
(1) Weighing 20g of coconut shell particle activated carbon, adding the coconut shell particle activated carbon into 280ml of deionized water, placing the coconut shell particle activated carbon into a 100 ℃ water bath kettle for washing, boiling for 35min, cooling to room temperature, filtering, discarding 30ml of primary filtrate, measuring the conductivity of the residual solution by using a conductivity tester, completely filtering the solution after the measurement is finished, adding 280ml of deionized water again, repeating the process, washing for 8 times, and drying at the drying temperature of 105-110 ℃;
(2) Weighing precursor compounds of redox active substances with mass ratio (1 g) of Fe cations to Ni cations: ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Dissolving the precursor compound in deionized water with the mass ratio of 1;
(3) Weighing 19g of the carrier treated in the step (1), adding the carrier into 30ml of the aqueous suspension solution prepared in the step (2), preparing a mixture of the activated carbon carrier and Fe and Ni oxides, and uniformly stirring the mixture by using a glass rod;
(4) Putting the uniform mixture obtained in the step (3) into an ultrasonic oscillator, and carrying out ultrasonic oscillation for 2 hours to uniformly load Fe and Ni on the activated carbon;
(5) Drying the activated carbon loaded with Fe and Ni obtained in the step (4), putting the dried activated carbon into a beaker, putting the beaker into an oven, and drying for 12 hours, wherein the drying is carried out in the air, and the drying temperature is 105-110 ℃;
(6) Putting the dried activated carbon loaded with the oxide precursor obtained in the step (5) into a reactor, calcining in a tubular furnace, heating the tubular furnace at the heating rate of 10 ℃/min for 55min, calcining at the temperature of 550 ℃ for 5h, and introducing 100ml/min nitrogen into the reactor all the time in the calcining process;
(7) And (3) after the reactor is cooled to normal temperature, taking out the loaded active carbon catalyst, and weighing for later use.
The change law of the conductivity during the pretreatment of the activated carbon carrier is shown in FIG. 3
Example 3
A method for preparing synthesis gas by electrocatalysis of methane-carbon dioxide comprises the following steps:
(1) Placing a catalyst (Fe and Ni loaded active carbon) in a reactor, placing the reactor in a tubular furnace, setting the furnace temperature at 400 ℃, heating rate at 10 ℃/min, opening a carrier gas 3 and a three-way valve 6, placing a flow controller 4, and setting the flow at 100ml/min to form a passage from a gas mixer 7 to a reactor 16;
(2) When the furnace temperature reaches a preset value, opening the reaction gases 1 and 2, simultaneously opening the three-way valve 5, setting the flow rates of the flow controllers 4 to be 50ml/min and 50ml/min respectively, mixing the reaction gases 1 and 2 with the carrier gas 3 in the gas mixer 7, and then entering the reactor 16;
(3) When the furnace temperature reaches a preset value, simultaneously turning on a direct-current high-voltage power supply, setting the current intensity to be 1mA, and carrying out CH 4 -CO 2 Reforming to produce synthesis gas, and feeding the reaction product into a chromatograph 15 for quantitative analysis.
Example 4
Repeating steps (1) - (3) with the difference that: setting the current intensity to be 3mA;
example 5
Repeating steps (1) - (3) with the difference that: step (3) setting the current intensity to be 5mA;
example 6
Repeating steps (1) - (3) with the difference that: step (3) setting the current intensity to be 7mA;
example 7
Repeating steps (1) - (3) with the difference that: and (3) setting the current intensity to be 9mA.
The data from 5 experiments from example 3 to example 7 are summarized. As shown in FIG. 4, each abscissa, corresponds to two bar graphs, and to the left, to CO 2 And the right side corresponds to CH 4 . Reforming reaction seeds CH under 5 different current intensities at the temperature of 400 DEG C 4 Conversion and CO 2 The conversion varies, and the data demonstrates that the electric field can reduce the temperature of the reforming reaction and can stimulate the generation of thermal electrons, during which carbon deposition can occurPlays a transition role, participates in the reforming reaction and realizes the cyclic transfer of carbon. As shown in FIG. 5, the number of surface micro-porous structures of the fresh catalyst (upper graph in FIG. 5) was not as large as that of the fresh catalyst after 200min catalysis at the current intensity of 9mA.
In conclusion, the reaction temperature of the device and the method is only 400 ℃, which is far lower than the reaction temperature of the conventional thermal catalysis at 700 ℃, the conversion rate of methane and carbon dioxide is good, the catalyst has good activity and stability, the system balance time is short, the operation is stable, and the error of the output data is small. Compared with the traditional heating catalytic equipment, the device and the method have the advantages of long running time and high cost.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by 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 (19)
1. The utility model provides a device of electrocatalysis methane-carbon dioxide system synthetic gas which characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
the device comprises a gas mixer, a direct-current high-voltage power supply, an electrode, a thermocouple, an electrode plate and a reaction device, wherein a catalyst is placed in the reaction device; the electrode plates are arranged above and below the catalyst; the thermocouple is arranged in the middle of the catalyst through the electrode plate; one end of the electrode is connected with the electrode plate, and the other end of the electrode is connected with a direct-current high-voltage power supply;
the gas supply device is connected with the gas inlet of the reaction device, and the gas inlet of the reaction device is positioned outside the space formed by the electrode plates; the gas supply device comprises a reaction gas supply device and a carrier gas supply device, and the reaction gas supply device comprises a methane supply device and a carbon dioxide supply device;
the temperature of the reaction device is 350-500 ℃;
fe. The preparation method of the Ni-doped carbon-based catalyst comprises the following specific steps:
heating activated carbon in water, cleaning and drying;
putting the dried activated carbon into a suspension solution of the Fe and Ni precursor;
drying and calcining the impregnated and loaded activated carbon to obtain a Fe and Ni doped carbon-based catalyst;
the washing times of the activated carbon are 3-15 times;
fe. The mass ratio of Fe and Ni precursors to water in the suspension solution of the Ni precursor is 1:3-4;
the mass ratio of the activated carbon to the suspension solution of the Fe precursor and the Ni precursor is 1:1-2;
the calcining temperature is 450-600 ℃, and the calcining time is 3-6h.
2. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 1, wherein: the reaction device is provided with an air outlet which is arranged at one end opposite to the air inlet.
3. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 1, wherein: the gas supply device also comprises a gas mixer which is respectively connected with the reaction gas supply device and the carrier gas supply device.
4. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 1, wherein: the temperature of the reaction device is 400-500 ℃.
5. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 1, wherein:
the washing times of the activated carbon are 5-10 times;
the water temperature of the activated carbon washing is 70-120 ℃;
the drying temperature of the washed activated carbon is 100-130 ℃, and the drying time is 10-16h.
6. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 5, wherein: the water temperature of the activated carbon washing is 80-110 ℃.
7. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 5, wherein: the drying temperature of the washed activated carbon is 105-110 ℃, and the drying time is 12-15h.
8. The apparatus for electrocatalytic methane-carbon dioxide synthesis gas production according to claim 1, wherein: fe. Fe and Ni precursors in the suspension solution of the Ni precursor are respectively nickel nitrate and iron nitrate;
and carrying out ultrasonic treatment during the process of mixing the activated carbon with the suspension solution of the Fe precursor and the Ni precursor, wherein the ultrasonic treatment time is 1-4h.
9. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 8, wherein: fe. The Fe and Ni precursors in the suspension solution of the Ni precursor are respectively Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O；
And carrying out ultrasonic treatment during the process of mixing the activated carbon with the suspension solution of the Fe precursor and the Ni precursor, wherein the ultrasonic treatment time is 2-3h.
10. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 1, wherein: fe. The mass ratio of Fe to Ni precursor to water in the suspension solution of the Ni precursor is 1;
the mass ratio of the activated carbon to the suspension solution of the Fe and Ni precursors is 1.5.
11. The apparatus for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 1, wherein: the calcining temperature is 500-600 ℃, and the calcining time is 4-6h.
12. A method for preparing synthesis gas by electrocatalysis of methane-carbon dioxide is characterized in that: the method comprises the following specific steps:
raising the temperature within the reaction apparatus;
introducing mixed gas of reaction gas and carrier gas into the reaction device;
the reaction gas is subjected to reforming reaction under the action of an electric field to obtain the synthesis gas.
13. The method for electrocatalytic methane-carbon dioxide synthesis gas production according to claim 12, wherein: the mass of nickel oxide supported on 1g of activated carbon was 0.005-0.025g, and the mass of iron oxide supported on 1g of activated carbon was 0.025-0.045g.
14. The method for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 13, wherein: the mass of the nickel oxide loaded on 1g of the activated carbon is 0.01-0.02g.
15. The method for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 13, wherein: the mass of the iron oxide loaded on 1g of the activated carbon is 0.03-0.04g.
16. The method for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 12, wherein: the current is direct current, and the current intensity is 2-10mA.
17. The method for electrocatalytic methane-carbon dioxide synthesis gas production according to claim 16, wherein: the current intensity is 3-9mA.
18. The method for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 12, wherein: the air inlet flow of the reaction device is 80-120 ml/min.
19. The method for electrocatalytic production of syngas from methane-carbon dioxide as set forth in claim 18, wherein: the air inlet flow of the reaction device is 90-11ml/min.
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