CN114180519A - Device and method for preparing hydrogen and nano carbon material by plasma decomposition coal bed gas reaction - Google Patents
Device and method for preparing hydrogen and nano carbon material by plasma decomposition coal bed gas reaction Download PDFInfo
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Abstract
The invention discloses a device and a method for preparing hydrogen and a nano carbon material by decomposing coal bed gas with plasma through a reaction. The device comprises a plasma reaction device, a hydrogen purification device and a high-purity hydrogen storage tank; the gas outlet of the plasma reaction device is connected with the gas inlet of the hydrogen purification device; a high-purity hydrogen gas outlet of the hydrogen purification device is connected with a gas inlet of the high-purity hydrogen storage tank; the tail gas outlet of the hydrogen purification device is connected with the gas inlet of the plasma reaction device; the plasma reaction device comprises a plasma excitation source, a vacuum reaction cavity and a material receiving disc; the vacuum reaction cavity is provided with an air inlet and an air outlet, and the take-up pan is placed at the bottom of the vacuum reaction cavity; the plasma excitation source of the plasma reaction device is any one of a hot filament, a direct current plasma jet arc and a microwave electromagnetic field. The device has the advantages of strong reaction controllability, flexible and various products, high product purity and additional value, zero discharge and no pollution.
Description
Technical Field
The invention relates to a device and a method for preparing hydrogen and a nano carbon material by decomposing coal bed gas with plasma through a reaction, and belongs to the field of efficient clean utilization of coal bed gas.
Background
The main component of coal bed gas (methane) is usually used as fuel or power generation, however, the fuel consumption is limited, and the power generation efficiency is low, so that most of the coal bed gas extracted at present is discharged into the atmosphere, which wastes resources and causes serious greenhouse effect and environmental pollution.
Methane in coal bed gas is an excellent hydrogen production raw material, and the traditional method generally utilizes steam reforming, partial oxidation or autothermal reforming of methane in coal bed gas to produce hydrogen. However, this invention is limited by the reaction equilibrium, the conversion is low, and the tail gas usually contains a large amount of CO, CO2And the gas, which still needs further treatment, otherwise will cause new environmental problems. Chinese patent ZL 200510022208.4 discloses a method for preparing hydrogen from coal bed gas, namely a method for preparing hydrogen from coal bed gas by steam reforming, the method is only suitable for preparing hydrogen from coal bed gas with 26-70% of methane content, and CO exist in reaction products2And unreacted methane. Chinese patent ZL 201711339654.7 discloses a coal bed gas deoxidation hydrogen production device and method, firstly, deoxidation catalyst is used to deoxidize coal bed gas, then CO is used to reduce high valence metal oxide, finally metal or low valence metal oxide obtained by reduction and steam are used to convert coal bed gas into hydrogen and CO2. However, the invention will produce CO2Directly into the atmosphere, environmental problems still remain.
The hydrogen production by coal bed gas cracking is to decompose carbon-containing gas sources such as methane and the like into hydrogen and carbon materials under high temperature, and CO are not discharged in the process2The method is the best choice for zero emission utilization of the coal bed gas. Chinese patent ZL 200810119203.7 discloses a method for preparing hydrogen and nanocarbon by low-temperature catalytic cracking of methane, in which hydrocarbons and methane (endothermic cracking) which release heat during cracking are subjected to catalytic cracking simultaneously in the presence of a catalyst to generate hydrogen and nanocarbon products. However, the invention takes methane as raw material and hydrocarbon gas which is exothermic in cracking must be added in the reaction process, so the cost is high; the generated hydrogen still contains methane component, and the purity is low; the catalyst can not be reused and the energy consumption is higher. Chinese patent ZL 20171020576.0 discloses a method for preparing hydrogen by catalytic cracking of methane in molten salt and a device for implementing the method, which is beneficial toThe catalyst is used for catalyzing methane to crack to produce hydrogen-rich gas and solid carbon, and the hydrogen and the solid carbon are obtained through a gas-solid separator. However, the invention utilizes the molten salt to carry out gas-solid separation, and needs higher energy consumption for preventing the molten salt from solidifying, and the device needs special design for preventing the molten salt from condensing and blocking the pipeline; the produced solid carbon is mixed with molten salt, catalyst, etc. and has a low purity even after solid-liquid separation. The invention discloses a device and a method for preparing hydrogen by catalytic cracking of natural gas or coal bed gas, which are disclosed by Chinese invention patent ZL 202010241533.4. However, the invention adopts one or more of molten metal, molten alloy, metal oxide, carbon material and rare earth compound as the catalyst, and the catalyst needs to be heated to a molten or high-temperature state, so that the energy consumption is high; the coal bed gas cracking reaction is carried out under the conditions of high air pressure (1-10 bar) and medium and low temperature (450-950 ℃), and the reaction efficiency is low; and an additional gas-solid separation device is required besides the main reaction device, so that the whole structure of the device is complex.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a device and a method for preparing hydrogen and a nano carbon material by decomposing coal bed gas with plasma through reaction.
The technical principle of the invention is as follows: the plasma reaction device mainly comprises a plasma excitation source, a vacuum reaction cavity and a material receiving disc, wherein the plasma excitation source is one of a hot filament, a microwave electromagnetic field and a direct current plasma jet arc.
When the hot filament is used as a plasma excitation source, the structure of the plasma reaction device is as follows: 1-10 layers of hot filaments are suspended in the vacuum reaction cavity, the hot filaments are connected to one or more direct current or alternating current power supplies arranged outside the vacuum reaction cavity, and a material receiving disc is placed close to the bottom of the vacuum reaction cavity; during reaction, the hot filament generates heat radiation to excite the coal bed gas introduced from the gas inlet and dissociate into H atom and active carbon radical (-CH)3、-C2H2, -CH, etc.).
When microwave electromagnetic field is adopted as plasma excitation source, plasma reaction deviceThe structure of the device is as follows: one side of the microwave transmission coupling mechanism is connected with a microwave source, and the other side of the microwave transmission coupling mechanism is connected with the vacuum reaction cavity; a microwave medium window is arranged between the microwave transmission coupling mechanism and the vacuum reaction cavity, so that the vacuum degree of the vacuum reaction cavity is maintained while the microwave energy is transmitted into the vacuum reaction cavity; a material receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom; in the reaction process, microwave energy generated by a microwave source is transmitted into the vacuum reaction cavity through the microwave transmission coupling mechanism and the microwave medium window, and is coupled and focused in the vacuum reaction cavity to form a high-energy electromagnetic field; the coal bed gas introduced from the gas inlet is excited by a high-energy electromagnetic field and is dissociated into H atoms and carbon-containing active groups (-CH)3、-C2H2, -CH, etc.).
When the direct current plasma jet arc is adopted as a plasma excitation source, the structure of the plasma reaction device is as follows: the top of the vacuum reaction cavity is provided with a plasma torch, and a receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom; the plasma torch consists of a cathode, an anode, a shielding case and a nozzle, namely, the innermost part is the cathode, the outer side of the cathode is sleeved with the anode, and the cathode and the anode are respectively connected to the cathode and the anode of a direct current/pulse adjustable high-voltage power supply; shielding cases made of insulating ceramics are sleeved between the cathode and the anode and outside the anode; a circular ring-shaped or funnel-shaped nozzle is embedded at the bottom of the anode; during reaction, the coal bed gas introduced from the gas inlet is excited by electric arc and dissociated into H atoms and active carbon-containing radicals (-CH)3、-C2H2and-CH, etc.) and forms a plasma arc jet under the action of the gas flow into the vacuum reaction chamber. Atomic H and carbon-containing reactive group (-CH) in plasma3、-C2H2to-CH, etc.) under a certain temperature condition to generate H by hydrogen abstraction reaction2And carbon particles, and the carbon particles sink to the receiving tray under the action of gravity to complete gas-solid separation; the reacted gas is output from a gas outlet and purified into high-purity H in a hydrogen purification device2And the carbon particles deposited on the take-up disc grow into the nano carbon material under the catalysis of the catalytic active component.
In the present invention, the main reactions that take place are as follows:
the invention provides a device for producing hydrogen and a nano-carbon material by plasma decomposition coal bed gas reaction, which mainly comprises a plasma reaction device, a hydrogen purification device and a high-purity hydrogen storage tank; the gas outlet of the plasma reaction device is connected with the gas inlet of the hydrogen purification device; a high-purity hydrogen gas outlet of the hydrogen purification device is connected with a gas inlet of the high-purity hydrogen storage tank; the tail gas outlet of the hydrogen purification device is connected with the gas inlet of the plasma reaction device; the plasma reaction device comprises a plasma excitation source, a vacuum reaction cavity and a material receiving disc; the vacuum reaction cavity is provided with an air inlet and an air outlet; the material receiving disc is placed at the bottom of the vacuum reaction cavity;
further, the plasma excitation source of the plasma reaction device can be any one of a hot filament, a direct current plasma jet arc and a microwave electromagnetic field;
further, when the hot filament is used as a plasma excitation source, the plasma reaction device has the following structure: an air inlet and an air outlet are respectively arranged at two sides of the vacuum reaction cavity, 1-10 layers of hot filaments are suspended in the vacuum reaction cavity, and a material receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom of the vacuum reaction cavity under the hot filaments; all the hot filaments are connected to one or more direct current or alternating current power supplies arranged outside the vacuum cavity; the hot filament is made of any one or more of tungsten, tantalum or molybdenum, and can be in any one of filament, plate, net, column or spring shape, and when arranged in multiple layers, each layer can be arranged in the same direction or in a crossed manner.
Further, the microwave electromagnetic field is used as a plasma excitation source, and the structure of the plasma reaction device is as follows: one side of the microwave transmission coupling mechanism is connected with a microwave source, and the other side of the microwave transmission coupling mechanism is connected with the vacuum reaction cavity; a microwave medium window is arranged between the microwave transmission coupling mechanism and the vacuum reaction cavity; the side surface of the vacuum reaction cavity is provided with an air inlet, the bottom of the vacuum reaction cavity is provided with an air outlet, and a material receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom of the vacuum reaction cavity.
Further, when the direct current plasma jet arc is used as a plasma excitation source, the structure of the plasma reaction device is as follows: the top of the vacuum reaction cavity is provided with a plasma torch, the bottom of the vacuum reaction cavity is provided with an air outlet, an air inlet is arranged at the upper part of the plasma torch, and a material receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom of the vacuum reaction cavity; the plasma torch consists of a cathode, an anode, a shielding case and a nozzle; the cathode is a needle point, a rod, a circle or a cylinder made of any one of tungsten, tantalum, molybdenum or graphite and is placed at the position of the central axis of the plasma torch; the anode is a sleeve made of any one of tungsten, tantalum, molybdenum or graphite and is sleeved outside the cathode; shielding cases made of insulating ceramics are sleeved between the cathode and the anode and outside the anode; a circular ring-shaped or funnel-shaped nozzle made of any one of tungsten, tantalum, molybdenum or graphite is embedded into the bottom of the anode; the cathode and the anode are respectively connected with the cathode and the anode of a direct current/pulse adjustable high-voltage power supply.
Furthermore, the material receiving disc is arranged at the bottom of the vacuum reaction cavity and is made of metal or alloy containing any one or more of catalytic components of Fe, Co, Ni, Cu, Mo, V, Zn, Cr and Mn.
Furthermore, the hydrogen purification device adopts one of pressure swing adsorption, membrane separation or palladium tube separation.
The invention provides a method for preparing hydrogen and a nano carbon material by a plasma decomposition coal bed gas reaction based on the device, wherein the desulfurized coal bed gas is excited into plasma in the plasma reaction device and reacts to generate hydrogen and carbon particles; purifying the reacted gas to obtain high-purity hydrogen, and circularly feeding the purified tail gas into a plasma reaction device until methane in the tail gas is completely decomposed; and the carbon particles are deposited on the take-up pan under the action of gravity, and generate the nano carbon material under the action of the catalytic active component.
The method is mainly realized by the following steps:
(1) plasma decomposition coal bed gas reaction
The desulfurized coal bed gas enters a vacuum reaction cavity of a plasma reaction device at a gas flow rate of 10 mL/min-30L/min, is excited and decomposed into plasma under the action of a plasma excitation source, and reacts at 400-1500 ℃ to generate hydrogen and carbon particles; the reacted gas is output through a gas outlet of the plasma reaction device, and the generated carbon particles are deposited on the receiving disc under the action of gravity, and form the nano carbon material under the action of the catalytic active component of the receiving disc.
(2) Purification of hydrogen
The gas reacted in the step (1) enters through an air inlet of a hydrogen purification device, is purified to obtain high-purity hydrogen with the purity of 99-99.99999%, and enters into a high-purity hydrogen storage tank through an air outlet of the hydrogen purification device and an air inlet of the high-purity hydrogen storage tank; the purified tail gas enters the plasma reaction device through a circulating gas pipeline connected between a tail gas outlet of the hydrogen purification device and a gas inlet of the plasma reaction device to further crack and catalyze the unreacted methane until the methane completely reacts.
(3) Collection of nanocarbon materials
And after the reaction is finished, opening the plasma reaction device, taking out the receiving disc, and collecting the nano carbon material in the receiving disc.
Further, the vacuum degree in a vacuum reaction cavity of the plasma reaction device is 1000-30000 Pa.
Further, the methane content in the coal bed gas is 30% -99.99%; the nano carbon material is one or more of activated carbon, carbon black, carbon nano tubes, graphene or onion carbon.
The invention has the beneficial effects that:
1) the methane cracking reaction in the high-purity H is carried out by utilizing a plurality of groups of glow discharges and a plurality of groups of hollow cathode effects2The reaction is more thorough, the product purity and the added value are high, and the finally discharged tail gas does not contain CO2And CO and the like, is clean, green and pollution-free, and is in accordance with the policy of 'carbon neutralization and carbon peak reaching'.
2) According to the invention, different nano carbon materials (one or a mixture of more of active carbon, carbon black, carbon nano tubes, graphene and onion carbon) can be obtained by adjusting the reaction temperature, the gas flow rate, the vacuum degree in the vacuum reaction cavity, the metal components of the take-up pan and the like, the reaction controllability is strong, and the products are flexible and various.
3) The invention is suitable for coal bed gas with various methane ratios, can also be used for hydrocarbon gas such as methane, ethane, acetylene and the like and gas containing hydrocarbon compounds such as natural gas, methane, coke oven gas and the like, and has the advantages of cheap raw material source, simple device structure and low cost. The device has strong reaction controllability and flexible and diverse products.
Drawings
FIG. 1 is a diagram of an apparatus for producing hydrogen and nanocarbon materials by plasma decomposition of coal bed gas according to the present invention;
FIG. 2 is a schematic structural diagram of a vacuum reaction chamber (with a hot filament plasma excitation source inside);
FIG. 3 is a schematic structural diagram of a plasma reaction apparatus using a hot filament as a plasma excitation source in embodiment 1 of the present invention;
FIG. 4 is a schematic structural diagram of a plasma reaction apparatus using a hot filament as a plasma excitation source in embodiment 2 of the present invention;
FIG. 5 is a schematic structural diagram of a plasma reaction apparatus using a microwave electromagnetic field as a plasma excitation source in embodiment 3 of the present invention;
FIG. 6 is a schematic structural diagram of a plasma reaction apparatus using a DC plasma jet arc as a plasma excitation source in embodiment 4 of the present invention;
in the figure: the device comprises a 1-plasma reaction device, a 2-hydrogen purification device, A3-high-purity hydrogen storage tank, a 11-vacuum reaction cavity, a 12-take-up pan, an A-hot filament plasma excitation source, an A1-8 layers of vertically crossed filament tantalum filaments, an A2-4 layers of forwardly arranged spring-shaped tungsten filaments, a 13-microwave source, a 14-microwave transmission coupling mechanism, a 15-microwave dielectric window, a 16-cathode, a 17-anode, an 18 shield cover and a 19-nozzle.
Detailed Description
In order that those skilled in the art will better understand the present invention, a more complete and complete description of the present invention is provided below in conjunction with the accompanying drawings and embodiments.
Example 1
Referring to fig. 1 to 3, a device for producing hydrogen and a nanocarbon material by plasma decomposition coal bed gas reaction mainly comprises a plasma reaction device 1, a hydrogen purification device 2 and a high-purity hydrogen storage tank 3; the plasma reaction device comprises a plasma excitation source, a vacuum reaction cavity 11 and a material receiving disc 12; the vacuum reaction cavity 11 is provided with an air inlet and an air outlet; the receiving tray 12 is placed at the bottom in the vacuum reaction cavity 11;
the gas outlet of the plasma reaction device 1 is connected with the gas inlet of the hydrogen purification device 2;
a high-purity hydrogen gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the high-purity hydrogen storage tank 3;
and a tail gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the plasma reaction device 1.
The plasma reaction device 1 adopts a hot filament plasma excitation source A, and 8 layers of filament-shaped tantalum filaments A1 which are vertically and crossly arranged are arranged and connected to two independent direct current power supplies; the material receiving disc 12 is arranged at the bottom of the vacuum reaction cavity 11 and is made of 316 stainless steel containing Fe, Ni, Mo and Cr catalytic active components; the hydrogen purification device 2 adopts a pressure swing adsorption technology.
The method for preparing the hydrogen and the nano carbon material by the plasma decomposition coal bed gas reaction is characterized by mainly comprising the following steps of:
(1) plasma decomposition coal bed gas reaction
Desulfurized coal bed gas (the methane accounts for 30 percent) enters a vacuum reaction cavity 11 of the plasma reaction device 1 at a gas flow rate of 10 mL/min, is excited and decomposed into plasma under the action of a hot filament plasma excitation source A1, and reacts at 400 ℃ and 1000 Pa to generate hydrogen and carbon particles; the reacted gas is output through the gas outlet of the plasma reaction device 1, and the generated carbon particles are deposited on the receiving disc 12 under the action of gravity, and generate the nano carbon black under the catalysis of the catalytic active components of Fe, Ni, Mo and Cr.
(2) Purification of hydrogen
The gas reacted in the step (1) enters through an air inlet of a hydrogen purification device 2 and is purified to obtain high-purity H with the purity of 99 percent2The gas enters the high-purity hydrogen storage tank 3 through a gas outlet of the hydrogen purification device 2 and a gas inlet of the high-purity hydrogen storage tank 3; the purified tail gas is circularly fed into the plasma reaction device 1 to further crack and catalyze the unreacted methane until the methane is completely reacted.
(3) Collection of nanocarbon materials
After the reaction is finished, the plasma reaction device 1 is opened, the receiving disc 12 is taken out, and the nano carbon black in the receiving disc is collected and stored.
Example 2
Referring to fig. 1, 2 and 4, an apparatus for producing hydrogen and a nanocarbon material by plasma decomposition coal bed gas reaction mainly comprises a plasma reaction apparatus 1, a hydrogen purification apparatus 2, and a high purity hydrogen storage tank 3; the plasma reaction device comprises a hot filament plasma excitation source A, a vacuum reaction cavity 11 and a material receiving disc 12; the vacuum reaction cavity 11 is provided with an air inlet and an air outlet; the receiving tray 12 is placed at the bottom in the vacuum reaction cavity 11;
the gas outlet of the plasma reaction device 1 is connected with the gas inlet of the hydrogen purification device 2;
a high-purity hydrogen gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the high-purity hydrogen storage tank 3;
and a tail gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the plasma reaction device 1.
The plasma reaction device 1 adopts a hot filament plasma excitation source A, 4 layers of spring-shaped tungsten filaments A2 which are arranged in the forward direction are arranged and are connected to a direct current power supply; the receiving disc 12 is arranged at the bottom of the vacuum reaction cavity 11 and is made of cast iron containing Fe catalytic active components; the hydrogen purification device 2 adopts a pressure swing adsorption technology.
The method for preparing the hydrogen and the nano carbon material by the plasma decomposition coal bed gas reaction is characterized by mainly comprising the following steps of:
(1) plasma decomposition coal bed gas reaction
The desulfurized coal bed gas (the methane accounts for 45 percent) enters a vacuum reaction cavity 11 of the plasma reaction device 1 at a gas flow rate of 100 mL/min, the methane in the desulfurized coal bed gas is excited and decomposed to form plasma, and hydrogen and carbon particles are generated by reaction when the reaction temperature reaches 600 ℃ and 5000 Pa; the reacted gas is output through the gas outlet of the plasma reaction device 1, and the generated carbon particles are deposited on the receiving disc 12 under the action of gravity, and generate a nano carbon material containing two components of nano activated carbon and nano carbon black under the catalysis of the Fe catalytic active component.
(2) Purification of hydrogen
The gas reacted in the step (1) enters through an air inlet of a hydrogen purification device 2 and is purified to obtain high-purity H with the purity of 99.9 percent2The gas enters the high-purity hydrogen storage tank 3 through a gas outlet of the hydrogen purification device 2 and a gas inlet of the high-purity hydrogen storage tank 3; the purified tail gas is circularly fed into a plasma reaction device 1 to further crack and catalyze the unreacted methaneTo complete reaction.
(3) Collection of nanocarbon materials
After the reaction is finished, the plasma reaction device 1 is opened, the receiving disc 12 is taken out, and the nano carbon material containing the nano activated carbon and the nano carbon black is collected and stored.
Example 3
Referring to fig. 1 and 5, an apparatus for producing hydrogen and nanocarbon materials by plasma decomposition coal bed gas reaction, referring to fig. 1 and 3, mainly comprises a plasma reaction device 1, a hydrogen purification device 2, a high purity hydrogen storage tank 3; the plasma reaction device comprises a plasma excitation source, a vacuum reaction cavity 11 and a material receiving disc 12; the vacuum reaction cavity 11 is provided with an air inlet and an air outlet; the receiving tray 12 is placed at the bottom in the vacuum reaction cavity 11;
the gas outlet of the plasma reaction device 1 is connected with the gas inlet of the hydrogen purification device 2;
a high-purity hydrogen gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the high-purity hydrogen storage tank 3;
and a tail gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the plasma reaction device 1.
Further, the plasma excitation source of the plasma reaction device 1 is a microwave electromagnetic field, and is provided with a microwave source 13, a microwave transmission coupling mechanism 14 and a microwave dielectric window 15; the receiving disc 12 is arranged at the bottom of the vacuum reaction cavity 11 and is made of red copper containing a Cu catalytic component; the hydrogen purification device 2 adopts a palladium tube separation technology.
The method for preparing the hydrogen and the nano carbon material by the plasma decomposition coal bed gas reaction is characterized by mainly comprising the following steps of:
(1) plasma decomposition coal bed gas reaction
The desulfurized coal bed gas (the methane accounts for 99.99 percent) enters a vacuum reaction cavity 11 of a plasma reaction device 1 at a gas flow rate of 1L/min, is excited and decomposed into plasma under the action of a microwave electromagnetic field plasma excitation source, and reacts at 1500 ℃ and 30000 Pa to generate hydrogen and carbon particles; the reacted gas is output through the gas outlet of the plasma reaction device 1, and the generated carbon particles are deposited on the material receiving disc 12 under the action of gravity, and form carbon nano tubes under the catalytic action of the Cu catalytic active component.
(2) Purification of hydrogen
The gas reacted in the step (1) enters through the gas inlet of the hydrogen purification device 2, is purified to obtain high-purity hydrogen with the purity of 99.99999 percent, and enters into the high-purity hydrogen storage tank 3 through the gas outlet of the hydrogen purification device 2 and the gas inlet of the high-purity hydrogen storage tank 3; the purified tail gas is circularly fed into the plasma reaction device 1 to further crack and catalyze the unreacted methane until the methane is completely reacted.
(3) Collection of nanocarbon materials
After the reaction is completed, the plasma reaction device 1 is opened, the take-up tray 12 is taken out, and the carbon nanotubes therein are collected.
Example 4
Referring to fig. 1 and 6, an apparatus for producing hydrogen and a nanocarbon material by plasma decomposition coal bed gas reaction mainly comprises a plasma reaction device 1, a hydrogen purification device 2, and a high purity hydrogen storage tank 3; the plasma reaction device comprises a plasma excitation source, a vacuum reaction cavity 11 and a material receiving disc 12; the vacuum reaction cavity 11 is provided with an air inlet and an air outlet; the receiving tray 12 is placed at the bottom in the vacuum reaction cavity 11;
the gas outlet of the plasma reaction device 1 is connected with the gas inlet of the hydrogen purification device 2;
a high-purity hydrogen gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the high-purity hydrogen storage tank 3;
and a tail gas outlet of the hydrogen purification device 2 is connected with a gas inlet of the plasma reaction device 1.
Further, the plasma excitation source of the plasma reaction device 1 is a plasma jet arc, and a plasma torch consisting of a cathode 16, an anode 17, a shielding case 18 and a nozzle 19 is arranged; the cathode 16 is a needle-point-shaped graphite rod; the anode 17 is a tungsten sleeve and is sleeved around the cathode 16; a shield 19 made of insulating ceramic is arranged between the cathode 16 and the anode 17; the nozzle 19 is annular tungsten and is embedded at the bottom end of the anode 17; the plasma torch is connected to a direct current/pulse adjustable high-voltage power supply, the negative pole of the power supply is connected with the cathode 16, and the positive pole of the power supply is connected with the anode 17; the receiving disc 12 is arranged at the bottom of the vacuum reaction cavity 11 and is made of pure Mo; the hydrogen purification device 2 adopts a pressure swing adsorption technology.
The method for preparing the hydrogen and the nano carbon material by the plasma decomposition coal bed gas reaction is characterized by mainly comprising the following steps of:
(1) plasma decomposition coal bed gas reaction
The desulfurized coal bed gas (the methane content is 90%) enters a vacuum reaction cavity 11 of the plasma reaction device 1 at a gas flow rate of 30L/min, is excited and decomposed into plasma under the action of a microwave electromagnetic field plasma excitation source, and reacts at 1000 ℃ and 10000 Pa to generate hydrogen and carbon particles; the reacted gas is output through the gas outlet of the plasma reaction device 1, and the generated carbon particles are deposited on the receiving disc 12 under the action of gravity, and form nano onion carbon under the catalytic action of the Mo catalytic active component.
(2) Purification of hydrogen
The gas reacted in the step (1) enters through the gas inlet of the hydrogen purification device 2, is purified to obtain high-purity hydrogen with the purity of 99.9%, and enters into the high-purity hydrogen storage tank 3 through the gas outlet of the hydrogen purification device 2 and the gas inlet of the high-purity hydrogen storage tank 3; the purified tail gas is circularly fed into the plasma reaction device 1 to further crack and catalyze the unreacted methane until the methane is completely reacted.
(3) Collection of nanocarbon materials
After the reaction is finished, the plasma reaction device 1 is opened, the receiving disc 12 is taken out, and the nano onion carbon in the receiving disc is collected.
It should be noted that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and the features of the embodiments and examples in the present application may be combined with each other without conflict. Any modification, equivalent replacement, or improvement made within the technical scope and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (10)
1. A device for preparing hydrogen and a nano carbon material by decomposing coal bed gas through plasma reaction is characterized in that: comprises a plasma reaction device, a hydrogen purification device and a high-purity hydrogen storage tank; the gas outlet of the plasma reaction device is connected with the gas inlet of the hydrogen purification device; a high-purity hydrogen gas outlet of the hydrogen purification device is connected with a gas inlet of the high-purity hydrogen storage tank; the tail gas outlet of the hydrogen purification device is connected with the gas inlet of the plasma reaction device; the plasma reaction device comprises a plasma excitation source, a vacuum reaction cavity and a material receiving disc; the vacuum reaction cavity is provided with an air inlet and an air outlet; the material receiving disc is placed at the bottom of the vacuum reaction cavity; the plasma excitation source of the plasma reaction system is any one of a hot filament, a direct current plasma jet arc and a microwave electromagnetic field.
2. The apparatus for producing hydrogen and nano-carbon material by plasma decomposition of coal bed gas according to claim 1, wherein: when the hot filament is used as a plasma excitation source, the structure of the plasma reaction device is as follows: an air inlet and an air outlet are respectively arranged at two sides of the vacuum reaction cavity, 1-10 layers of hot filaments are suspended in the vacuum reaction cavity, and a material receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom of the vacuum reaction cavity under the hot filaments; all the hot filaments are connected to one or more DC or AC power supplies arranged outside the vacuum chamber.
3. The apparatus for producing hydrogen and nano-carbon material by plasma decomposition of coal bed gas according to claim 2, wherein: the hot filament is made of any one metal or alloy consisting of a plurality of metals of tungsten, tantalum or molybdenum, is in any one shape of filiform, plate-shaped, reticular, columnar or spring shape, and is in sequential or crossed arrangement of each layer when arranged in multiple layers.
4. The apparatus for producing hydrogen and nano-carbon material by plasma decomposition of coal bed gas according to claim 1, wherein: the microwave electromagnetic field is used as a plasma excitation source, and the structure of the plasma reaction device is as follows: one side of the microwave transmission coupling mechanism is connected with a microwave source, and the other side of the microwave transmission coupling mechanism is connected with the vacuum reaction cavity; a microwave medium window is arranged between the microwave transmission coupling mechanism and the vacuum reaction cavity; the side surface of the vacuum reaction cavity is provided with an air inlet, the bottom of the vacuum reaction cavity is provided with an air outlet, and a material receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom of the vacuum reaction cavity.
5. The apparatus for producing hydrogen and nano-carbon material by plasma decomposition of coal bed gas according to claim 1, wherein: when the direct current plasma jet arc is used as a plasma excitation source, the structure of the plasma reaction device is as follows: the top of the vacuum reaction cavity is provided with a plasma torch, the bottom of the vacuum reaction cavity is provided with an air outlet, an air inlet is arranged at the upper part of the plasma torch, and a material receiving disc with the shape close to the bottom of the vacuum reaction cavity is arranged at the position close to the bottom of the vacuum reaction cavity; the plasma torch consists of a cathode, an anode, a shielding case and a nozzle.
6. The apparatus for producing hydrogen and nano-carbon material by plasma decomposition of coal bed gas according to claim 5, wherein: the cathode is a needle point, a rod, a circle or a cylinder made of any one of tungsten, tantalum, molybdenum or graphite and is placed at the position of the central axis of the plasma torch; the anode is a sleeve made of any one of tungsten, tantalum, molybdenum or graphite and is sleeved outside the cathode; shielding cases made of insulating ceramics are sleeved between the cathode and the anode and outside the anode; a circular ring-shaped or funnel-shaped nozzle made of any one of tungsten, tantalum, molybdenum or graphite is embedded into the bottom of the anode; the cathode and the anode are respectively connected with the cathode and the anode of a direct current/pulse adjustable high-voltage power supply.
7. The apparatus for producing hydrogen and nano-carbon material by plasma decomposition of coal bed gas according to claim 1, wherein: the material receiving disc is arranged at the bottom of the vacuum reaction cavity and is made of metal or alloy containing any one or more of catalytic components of Fe, Co, Ni, Cu, Mo, V, Zn, Cr and Mn.
8. The apparatus for producing hydrogen and nano-carbon material by plasma decomposition of coal bed gas according to claim 1, wherein: the hydrogen purification device adopts one of pressure swing adsorption, membrane separation or palladium tube separation.
9. A method for preparing hydrogen and a nano carbon material by plasma decomposition coal bed gas reaction, which adopts the device for preparing hydrogen and a nano carbon material by plasma decomposition coal bed gas reaction as claimed in any one of claims 1 to 8, and is characterized by comprising the following steps:
(1) plasma decomposition coal bed gas reaction
The desulfurized coal bed gas enters a vacuum reaction cavity of a plasma reaction device at a gas flow rate of 10 mL/min-30L/min, is excited and decomposed into plasma under the action of a plasma excitation source, and reacts at 400-1500 ℃ to generate hydrogen and carbon particles; the reacted gas is output through a gas outlet of the plasma reaction device, and the generated carbon particles are deposited on the receiving disc under the action of gravity, and form a nano carbon material under the action of a catalytic active component of the receiving disc;
(2) purification of hydrogen
The gas reacted in the step (1) enters through an air inlet of a hydrogen purification device, is purified to obtain high-purity hydrogen with the purity of 99-99.99999%, and enters into a high-purity hydrogen storage tank through an air outlet of the hydrogen purification device and an air inlet of the high-purity hydrogen storage tank; the purified tail gas enters the plasma reaction device through a circulating gas pipeline connected between a tail gas outlet of the hydrogen purification device and a gas inlet of the plasma reaction device to further crack and catalyze the unreacted methane until the methane completely reacts;
(3) collection of nanocarbon materials
And after the reaction is finished, opening the plasma reaction device, taking out the receiving disc, and collecting the nano carbon material in the receiving disc.
10. The method for producing hydrogen and nanocarbon materials by plasma decomposed coalbed methane reaction according to claim 9, wherein: the vacuum degree in a vacuum reaction cavity of the plasma reaction device is 1000-30000 Pa;
the proportion of methane in the coal bed gas is 30% -99.99%; the nano carbon material is one or more of activated carbon, carbon black, carbon nano tubes, graphene or onion carbon.
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