WO2014051366A1 - Reformeur à plasma et à micro-ondes - Google Patents

Reformeur à plasma et à micro-ondes Download PDF

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Publication number
WO2014051366A1
WO2014051366A1 PCT/KR2013/008657 KR2013008657W WO2014051366A1 WO 2014051366 A1 WO2014051366 A1 WO 2014051366A1 KR 2013008657 W KR2013008657 W KR 2013008657W WO 2014051366 A1 WO2014051366 A1 WO 2014051366A1
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reaction space
supply pipe
plasma
carbon dioxide
hydrocarbon
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PCT/KR2013/008657
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English (en)
Korean (ko)
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홍용철
천세민
조성윤
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한국기초과학지원연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/342—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J7/00—Apparatus for generating gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0881—Two or more materials
    • B01J2219/0883—Gas-gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0892—Materials to be treated involving catalytically active material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0222—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0861—Methods of heating the process for making hydrogen or synthesis gas by plasma

Definitions

  • the present invention relates to a microwave plasma reformer, and more particularly, by reforming methane (CH 4 ) and carbon dioxide (CO 2 ) injected through the plasma (P) as a main component of hydrogen (H 2 ) and carbon monoxide (CO)
  • the present invention relates to a plasma reformer for reforming a synthesis gas.
  • Synthetic gas which is a mixture of hydrogen and carbon monoxide, is an important medium for synthesizing chemical raw materials such as ammonia, methanol, acetic acid, DME (DiMethyl Ether), synthetic gasoline and diesel, and environmentally clean fuels.
  • various molar ratios of hydrogen and carbon monoxide H 2 / CO
  • a molar ratio of 2/1 is required for synthesizing methanol
  • a molar ratio of 1/1 is required for synthesizing acetic acid, Methyl Formate, or DME.
  • syngas is made from coal, petroleum, natural gas, biomass and even organic wastes, but at present, natural gas is the largest source for syngas production. Source is increasingly used to produce syngas for the cheapest and most environmentally friendly reasons.
  • Techniques for producing syngas using natural gas include steam reforming (wet reforming) of methane, partial oxidation of methane, carbon dioxide reforming (dry reforming) of methane, and combinations of steam reforming and carbon dioxide reforming of methane.
  • steam reforming wet reforming
  • methane partial oxidation of methane
  • carbon dioxide reforming dry reforming
  • wet reforming This process is commonly referred to as wet reforming and the hydrogen / carbon monoxide molar ratio is 3 or more, and wet reforming is suitable for ammonia synthesis but requires extra hydrogen in methanol and many other synthetic processes. On the other hand, at least one mole of methane is required to make one mole of carbon monoxide in a wet process reaction.
  • CH 4 -CO 2 reforming not only reduces methane consumption, but also draws attention as a very attractive syngas production process because of the use of carbon dioxide.
  • CH 4 -CO 2 reformation requires 1 ⁇ 2 moles of methane to produce 1 mole of carbon monoxide, since carbon dioxide is also a carbon source.
  • CH 4 -CO 2 reforming has a hydrogen / carbon monoxide ratio of 1/1, but the hydrogen / carbon monoxide ratio can be controlled relatively easily by controlling the methane / carbon dioxide ratio in the feed of the process. Therefore, syngas from CH 4 -CO 2 reforming can be used in acetic acid or Methyl Formate manufacturing processes, as well as satisfying the hydrogen / carbon monoxide molar ratios needed to produce various materials when combined with wet processes.
  • the CH 4 -CO 2 catalytic reforming process is injected into the Tubiform fixed bed reactor filled with methane and carbon dioxide in the catalytic reaction process and the heat energy required for the reaction is supplied from the combustion energy of natural gas outside the reactor. do.
  • the CH 4 -CO 2 catalytic reforming reactor can be used with a methane wet reforming reactor, the biggest barrier to the CH 4 -CO 2 catalytic reforming process from the laboratory scale to the commercial scale is the catalyst deactivation. It is the carbon deposition of the catalyst surface which becomes a cause.
  • the plasma CH 4 -CO 2 reforming process was performed under very limited conditions using arc discharge. Compared with the catalytic reforming process, the plasma CH 4 -CO 2 reforming reaction with electron induction and thermochemical reactions showed high conversion and selectivity and no carbon deposition problems. Therefore, despite the problem of energy use of plasma generation, there has been an increasing interest in continuous research over the last decade.
  • Patent Document 1 Korean Unexamined Patent Publication No. 2010-0017757 (2010.02.16), Method for producing a synthesis gas
  • the present invention was created to solve the above-mentioned problems, an object of the present invention is to uniformly mix the plasma generated in the reaction space and each gas injected into the inside, and to stably maintain the flame to be burned It is to provide a microwave plasma reformer.
  • Another object of the present invention is to combine the plasma wet process by injecting steam (H 2 O) to the dry reforming process using the plasma to control the hydrogen / carbon monoxide ratio while reducing the amount of electrical energy for the plasma to control various chemicals It is to provide a microwave plasma reformer that can be produced.
  • Another object of the present invention is to modify the methane (CH 4 ) and carbon dioxide (CO 2 ) injected through the plasma to produce a synthesis gas mainly composed of hydrogen (H 2 ) and carbon monoxide (CO), It is to provide a microwave plasma reformer that can reduce consumption and increase carbon dioxide consumption significantly.
  • Microwave plasma reformer for achieving the above object, by modifying the methane (CH 4 ) and carbon dioxide (CO 2 ) injected through the plasma (P) to hydrogen (H 2 ) and carbon monoxide (CO).
  • a reaction space 111 for generating the plasma P is formed therein, and a methane supply pipe for injecting the methane into the reaction space 111.
  • body parts 110 each having a carbon dioxide supply pipe 113 for injecting the carbon dioxide into the reaction space 111;
  • a discharge tube 120 mounted in the reaction space 111 of the body 110 and receiving a microwave of a preset frequency to generate a plasma in the reaction space 111;
  • a waveguide 135 fastened to the body 110 to be connected to the discharge tube 120 and receiving the microwaves and applying the microwaves to the discharge tube 120;
  • a hydrocarbon body supply pipe 140 disposed above the body part 110 and supplying a hydrocarbon body to the inside of the reaction space 111;
  • a chamber part 150 disposed inside the upper part of the body part 110 and protruding inwardly along a circumference to reduce an inner diameter of the reaction space 111.
  • a ring-shaped chamber space portion 151 through the circumference is formed in the chamber portion 150, the hydrocarbon supply pipe 140 is extended in the form to penetrate the body portion 110 In communication with the chamber space 151, the chamber 150 is connected to the inside of the chamber space 151 and the interior of the reaction space 111 by the hydrocarbon supply pipe 140 through the A plurality of split supply pipes 152 for injecting hydrocarbons injected into the chamber space 151 into the reaction space 111 may be spaced apart at regular intervals.
  • the split supply pipe 152, the chamber space 151 and the reaction space 111, the interior of the communication with each other, the end of the reaction space portion 111 is opened in the chamber portion 150 It may be formed on the protruding tip surface 153 of the).
  • the split supply pipe 152 may have a diameter smaller than the diameter of the hydrocarbon body supply pipe 140 and the chamber space portion 151.
  • the hydrocarbon body supply pipe 140 is formed in the form of a tangent (Tangent Line) with respect to the peripheral surface of the body portion 110, the hydrocarbon body supplied from the outside of the inner wall surface of the chamber space (151) ( Guided by 154 to form a vortex may be injected into the chamber space 151.
  • the split supply pipe 152 is formed in a tangent line shape with respect to the circumferential surface of the chamber portion 150, the hydrocarbon body injected from the chamber space portion 151 is the chamber portion 150 It may be guided by the front end surface 153 or the inner wall surface 115 of the body portion 110 to form a vortex and may be injected into the reaction space 111.
  • the split supply pipe 152 is disposed in a state inclined at a predetermined angle in the downward direction in the chamber portion 150 to inject the vortexed hydrocarbon body while descending into the reaction space 111. have.
  • the carbon dioxide supply pipe 113 is disposed around the side of the body portion 110, the reaction space portion 111 is disposed in an inclined state at an angle in the upper direction in the body portion 110. While vortexing carbon dioxide can be injected into the interior of the.
  • the carbon dioxide supply pipe 113 is formed in a tangent line shape with respect to the circumferential surface of the body portion 110, so that carbon dioxide supplied from the outside is inner wall surface 115 of the body portion 110. Guided by to form a vortex and flows into the reaction space 111 may be mixed with the plasma and methane and react.
  • hydrocarbons supplied to the hydrocarbon supply pipe 140 may be gaseous ethane, propane, ethylene, butane or liquid DME, gasoline, diesel, kerosene, bunker C oil, refined waste oil or solid state. It may be any one of coal and biomass.
  • the hydrocarbon body supply pipe 140 may inject a mixture of the hydrocarbon body and methane into the reaction space 111.
  • the carbon dioxide supply pipe 113 may inject a mixed gas of carbon dioxide and methane mixed into the reaction space 111.
  • the carbon dioxide supply pipe 113 injects a mixture of carbon dioxide and air or carbon dioxide and steam into the reaction space 111, or surrounds the body 110 with air or steam.
  • Supply pipes to be injected into the reaction space 111 may be formed separately.
  • an expansion space 170 may be formed at an upper end of the body 110 so that an inner diameter thereof is extended toward an upper direction.
  • the inclined surface of the expansion space 170 is formed to protrude upward, a plurality of flame induction blades 171 extending in the outward direction from the center of the body portion 110 are spaced at regular intervals and to be disposed radially Can be.
  • microwave plasma reformer According to the microwave plasma reformer according to the present invention,
  • the plasma (P) flame generated by protruding inwardly along the circumference in the upper inner part of the body part to reduce the pressure inside the reaction space where the reforming reaction occurs through the chamber to reduce the inner diameter of the reaction space.
  • reforming efficiency can be improved by mixing injected methane, carbon dioxide, a hydrocarbon body, etc. at high pressure.
  • the hydrocarbon material supplied through the hydrocarbon material supply pipe is branched through a plurality of split supply pipes and dispersed and injected into the reaction space part, the reforming efficiency is further improved by uniformly mixing the plasma P and the respective gas streams. You can increase it.
  • the split supply pipe is formed in a tangential form with respect to the circumferential surface of the chamber part, it is vortexed and injected into the reaction space part, so that the plasma P and the respective gas streams can be efficiently mixed and stably reacted chemically.
  • the high temperature plasma flame can protect the inner chamber surface of the discharge chamber portion, the discharge tube and the body portion.
  • the split supply pipe is inclined at a predetermined angle in the downward direction in the chamber portion to inject the vortexed hydrocarbon body while downward, and the carbon dioxide supply pipe for injecting carbon dioxide is inclined at a predetermined angle in the upper direction in the body portion
  • the upward air flow by the carbon dioxide injected from the carbon dioxide supply pipe acts as a forward vortex (Conventional Vortex Flow) with respect to the discharge direction of the reformed syngas
  • the airflow by the injected hydrocarbons acts as a reverse vortex flow with respect to the discharge direction of the reformed syngas, and the interaction of each gas flow causes plasma, carbon dioxide, methane and hydrocarbons to interact with each other in the reaction space.
  • a time that can be reacted and modified This modification of the efficiency is maximized while increasing.
  • the consumption of methane required to generate the synthesis gas can be reduced and the consumption of carbon dioxide can be greatly increased. That is, by using carbon dioxide, a global warming material, as a raw material, the carbon dioxide can be reduced.
  • 1 and 2 is a schematic view showing the configuration of a reformer using a conventional catalytic reformer
  • FIG. 3 is a cross-sectional view showing the configuration of a microwave plasma reformer according to a preferred embodiment of the present invention.
  • Figure 4 is a cross-sectional view showing the operation principle of the carbon dioxide is vortex injected as the carbon dioxide supply pipe is disposed in a tangential form with the body portion according to an embodiment of the present invention
  • FIG. 5 is a schematic diagram showing the configuration of the microwave supply unit according to a preferred embodiment of the present invention.
  • FIG. 6 is a cross-sectional view illustrating an operation principle in which the hydrocarbon is vortexed and injected as the hydrocarbon supply pipe and the split supply pipe are tangentially disposed in the body part and the chamber part according to the preferred embodiment of the present invention
  • Figure 7 is a cross-sectional view showing a configuration in which the divided supply pipe is inclined downward in the chamber portion according to a preferred embodiment of the present invention
  • FIGS. 8 and 9 are a perspective view and a plan view showing the configuration of the expansion space according to a preferred embodiment of the present invention.
  • FIG. 10 is a schematic diagram showing a state in which a photocatalyst is applied to a wall of a body of a plasma reformer according to a preferred embodiment of the present invention or a photocatalyst is filled in a wall thereof;
  • FIG. 11 is a graph showing the fraction of non-thermal carbon dioxide discharge energy transferred from plasma (P) electrons to various excitation paths (channels) of carbon dioxide molecules according to an exemplary embodiment of the present invention.
  • FIG. 12 is a graph showing an optical emission spectrum of pure CO 2 plasma (P) according to a preferred embodiment of the present invention.
  • the microwave plasma reformer according to a preferred embodiment of the present invention (hereinafter referred to as 'plasma reformer 100') is modified by hydrogen (CH 4 ) and carbon dioxide (CO 2 ) through plasma (P).
  • 'plasma reformer 100' is modified by hydrogen (CH 4 ) and carbon dioxide (CO 2 ) through plasma (P).
  • the plasma (P) generated in the reaction space 111 and the respective gases injected into the interior are uniformly mixed and burned.
  • the body portion 110, the discharge tube 120, the waveguide 135, the hydrocarbon supply tube 140, and the chamber portion 150 As shown in FIGS. 3 to 9, the body portion 110, the discharge tube 120, the waveguide 135, the hydrocarbon supply tube 140, and the chamber portion 150. It is provided including.
  • the body portion 110 is a component for forming a base of the plasma reformer 100 according to a preferred embodiment of the present invention
  • the reaction space portion 111 in which the plasma P is generated is formed
  • the methane supply pipe 112 for injecting the methane into the reaction space 111 and the carbon dioxide supply pipe 113 for injecting the carbon dioxide into the reaction space 111 are respectively formed.
  • the carbon dioxide supply pipe 113 as shown in Figure 4 is spaced at equal intervals along the circumference of the body portion 110 is formed a plurality, tangent to the circumferential surface of the body portion 110 And the carbon dioxide supplied from the outside is guided by the inner wall surface 115 of the body portion 110 to form a vortex and flows into the reaction space 111 to form the plasma P and It may be provided to react with and intermix with methane.
  • the carbon dioxide supply pipe 113 is disposed in an inclined state at an angle upward in the body portion 110 as shown in FIG. 3 and is vortexed while being upwardly inside the reaction space 111. Carbon dioxide can be injected.
  • the air flow by the carbon dioxide injected from the carbon dioxide supply pipe 113 acts as a forward vortex (Conventional Vortex Flow) with respect to the discharge direction of the reformed synthesis gas, the carbon dioxide air flow injected into the lower portion of the plasma (P) By increasing the intensity, the plasma and carbon dioxide may be mixed more smoothly.
  • the carbon dioxide supply pipe 113 may inject a mixed gas of carbon dioxide and gaseous hydrocarbons (for example, methane) into the reaction space 111.
  • a mixed gas of carbon dioxide and gaseous hydrocarbons for example, methane
  • the carbon dioxide supply pipe 113 may inject a mixture of carbon dioxide and air, oxygen, or carbon dioxide and steam into the reaction space 111, and separately from the carbon dioxide supply pipe 113.
  • a supply tube (not shown) for injecting air, oxygen, or steam into the reaction space 111 may be formed around the body 110 or the discharge tube 120.
  • the carbon dioxide and air or oxygen are mixed with each other and injected into the carbon dioxide supply pipe 113 and supplied to the plasma formed inside the reaction space 111 to reform the temperature of the reactor through a partial oxidation or combustion process of methane (inside the reactor). Temperature can be maintained, and the production of carbon monoxide and hydrogen can be increased through the partial oxidation of methane by injecting the steam (H 2 O) (Ratio of H 2 O / CO 2 > 1). have. In addition, the ratio of H 2 / CO can be controlled by controlling the steam at all times.
  • the body portion 110 is preferably formed of a refractory insulation material so as not to be damaged or damaged by the high temperature of the high-temperature, high-pressure plasma (P) and flame generated inside.
  • P high-pressure plasma
  • the plasma reformer 100 by filling the photocatalyst in the inner wall or the inside of the body portion 110 to form a catalytic reaction space, it is possible to increase the reforming efficiency after plasma reforming.
  • FIG. 10 is a schematic view showing a state where the photocatalyst is filled in the inner wall or the inside of the body portion 110 according to the preferred embodiment of the present invention.
  • a general photocatalyst (ZnO, TiO2, etc.) is normally excited when subjected to energy of 3.2 eV to act as a photocatalyst.
  • most of the Vibrational Excitation modes excite carbon dioxide at an energy of 0.5 eV or more and emit as much light as the corresponding energy descends to the ground state.
  • the reforming efficiency can be improved by filling the photocatalyst on the inner wall or the inside of the plasma reformer (100,200), and as shown in FIG. 12, pure carbon dioxide plasma emits light of 300-400 nm ( ⁇ 3.2 eV) while for the same reason as described above.
  • the photocatalyst can be excited to enhance the modification effect.
  • the catalyst that can be filled in the body portion 110 is as shown in Table 1 below.
  • the discharge tube 120 is mounted in the reaction space 111 of the body portion 110, and receives a microwave of a predetermined frequency to generate a plasma in the reaction space 111, cylindrical It is formed on the vertically disposed on the inner wall surface 115 of the body portion 110 to form a concentric circle with the reaction space 111.
  • the position of the central axis of the discharge tube 120 depends on the microwave frequency input from the waveguide 135 and the waveguide 135, preferably 1/4 of the tube wavelength.
  • the waveguide 135 is fastened to the body 110 so as to be connected to the discharge tube 120, and is a component that receives the microwave and applies it to the discharge tube 120, the microwave supply unit as shown in FIG.
  • the microwave generated from the 130 is provided to be applied to the discharge tube 120.
  • the microwave supply unit 130 outputs microwaves oscillated by the high frequency oscillator 131 and the microwaves oscillated by the high frequency oscillator 131 by receiving driving power supplied from the outside and impedance mismatch.
  • the circulator 132 for protecting the high frequency oscillator 131 by extinguishing microwave energy reflected by the power source, a power monitor 133 disposed at the rear end of the circulator 132 and monitoring power, and an output from the circulator 132.
  • Including the tuner 134 and the waveguide 135 so that the electric field induced by the microwave is maximized in the discharge tube 120 by inducing impedance matching by adjusting the intensity of the incident wave and the reflected wave of the microwave. do.
  • the hydrocarbon supply pipe 140 is a component for supplying a hydrocarbon to the plasma P generated by the reaction space 111 by injecting a hydrocarbon into the reaction space 111, the body portion ( It is disposed above the 110 and supplies a hydrocarbon to the inside of the reaction space 111.
  • the hydrocarbon body supply pipe 140 like the carbon dioxide supply pipe 113 described above, at least one spaced apart at equal intervals along the circumference of the body portion 110 is formed, as shown in FIG. It is formed in the form of a tangent (Tangent Line) with respect to the peripheral surface of the body portion 110, the hydrocarbon body supplied from the outside is guided by the inner wall surface 115 of the body portion 110 to form a vortex and the reaction space While flowing into the unit 111, the carbon dioxide, plasma, and methane may be mixed with and reacted with each other.
  • tangent Tangent Line
  • the hydrocarbons supplied from the outside are guided by the inner wall surface 115 of the discharge tube 120 or the body portion 110 to form a vortex and flow into the reaction space 111 to be mixed with the plasma and react with each other.
  • the carbon dioxide, methane, plasma and hydrocarbons can be more uniformly mixed in the reaction space 111 and react chemically stably, and further increase the strength of the air flow vortexed in the reaction space 111. have.
  • the hydrocarbon supply pipe 140 is disposed in an inclined state at a predetermined angle in the downward direction in the chamber part 150 to vortex while descending into the reaction space 111. It is preferred to be provided to inject the carbon dioxide.
  • the ascending air flow by the carbon dioxide injected from the carbon dioxide supply pipe 113 acts as a forward vortex (Conventional Vortex Flow) with respect to the discharge direction of the modified synthesis gas, the hydrocarbon body injected from the hydrocarbon body supply pipe 140
  • the downward air flow by the gas acts as a reverse vortex (Reverse Vortex Flow) with respect to the discharge direction of the reformed synthesis gas, the plasma flame and carbon dioxide, methane and hydrocarbons in the reaction space 111 by the interaction of each gas flow Increasing the time that can be reacted and reformed can maximize the efficiency of the reforming.
  • the hydrocarbon is an organic compound mainly containing carbon and hydrogen, and means a hydrocarbon compound of gas, liquid, and solid.
  • the hydrocarbon body any one of gaseous methane, ethane, propane, ethylene, butane or liquid DME, gasoline, diesel, kerosene, bunker C oil, refined waste oil or solid coal, biomass Can be used.
  • a liquid or solid hydrocarbon body may be used as described above, but the mixing efficiency of plasma (P), flame, and carbon dioxide, and the reaction space part during combustion ( It is preferable to use a gaseous hydrocarbon body so as to minimize the stacking of the burned combustion oxide generated when the hydrocarbon body is burned on the inner wall of the 111.
  • the hydrocarbon body supply pipe 140 is provided so as to inject a mixture of the hydrocarbon body and methane into the plasma P formed inside the reaction space 111 when methane is not used as the hydrocarbon body. Can be.
  • the plasma formed in the reaction space 111 may not be maintained or may be unstable, so that the methane is mixed with the hydrocarbon body to supply a hydrocarbon body supply pipe ( 140 may be injected into the plasma.
  • the hydrocarbon body supply pipe 140, the carbon dioxide supply pipe 113 is formed in a form that is in contact with the chamber portion 150 in the same direction as the direction tangential to the body portion 110, the carbon dioxide supply pipe 113 By vortexing inside the reaction space 111 and allowing the hydrocarbon body to vortex and inject in the same direction as the injection direction of the injected carbon dioxide, further increasing the intensity of the vortexed airflow to cause plasma (P), flame and each gas flow Can be mixed at high pressure.
  • plasma plasma
  • the hydrocarbon body supply pipe 140 is formed in a form in which the carbon dioxide supply pipe 113 is tangential to the chamber portion 150 in a direction opposite to the direction tangential to the body portion 110, thereby providing the carbon dioxide supply pipe (
  • the hydrocarbon body is vortexed and injected in a direction opposite to the injection direction of the injected carbon dioxide, the air flow and the hydrocarbon of the carbon dioxide vortexed inside the reaction space 111
  • the airflow of the sieves may collide to increase the mixing ratio between the plasma P, the flame induction blade 171 and the gas streams, thereby further increasing the reforming reaction.
  • the hydrocarbon body supply pipe 140 the air flow of the hydrocarbon body is formed as the injection direction of the hydrocarbon body which is supplied to the inside of the reaction space 111 directly below in the reaction space 111
  • the reforming reaction time by the plasma P may be increased by injecting to a deep position inside the plasma P generated in the reaction space 111.
  • the chamber part 150 is a component that reduces the inner diameter of the reaction space 111 to generate a pressure change inside the reaction space 111 in which a reforming reaction occurs, and an upper inner side of the body 110.
  • the inner space of the reaction space 111 is partially formed to protrude inwardly along the circumference.
  • the chamber 150 is formed in a ring-shaped chamber space 151 through the circumference of the chamber 150, wherein the hydrocarbon supply pipe 140 has a body portion ( It extends in the form to penetrate through the 110 and communicates with the chamber space 151, the inside of the chamber space 151 and the reaction space 111 is in communication with the chamber portion 150 by the hydrocarbon
  • a plurality of split supply pipes 152 for injecting hydrocarbons injected into the chamber space 151 through the sieve supply pipe 140 into the reaction space 111 are spaced apart at regular intervals.
  • the divided supply pipe 152 communicates with the inside of the chamber space 151 and the reaction space 111, and ends open into the reaction space 111. Is preferably formed on the protruding end surface 153 of the chamber portion 150.
  • the split supply pipe 152 is formed to have a diameter smaller than the diameter of the hydrocarbon body supply pipe 140 and the chamber space 151, relative to the airflow of the hydrocarbon body supplied through the hydrocarbon body supply pipe 140 Hydrocarbons can be injected while pressurizing toward the reaction space 111 at a high pressure.
  • the hydrocarbon material supplied through the hydrocarbon material supply pipe 140 is branched through the plurality of split supply pipes 152 and dispersed and injected into the reaction space 111.
  • the plasma P and each gas are injected.
  • the overall efficiency of the reforming can be further increased by evenly mixing the streams.
  • the split supply pipe 152 is formed in a tangent line with respect to the circumferential surface of the chamber part 150, and hydrocarbons are injected from the chamber space part 151. It is preferable that the sieve is guided by the front end surface 153 of the chamber part 150 or the inner wall surface 115 of the body part 110 to form a vortex and injected into the reaction space 111.
  • the plasma P and the gas streams in the reaction space 111 may be more effectively mixed with each other, thereby stably chemically reacting, as well as the plasma chamber 150 having a high-temperature plasma flame and the discharge tube 120. And the inner wall surface 115 of the body portion 110 can be protected.
  • the split supply pipe 152 is disposed in an inclined state at a predetermined angle in the downward direction in the chamber part 150 and is vortexed downward in the reaction space 111. It is preferable to spray the hydrocarbon body which becomes.
  • the split supply pipe 152 sprays the vortexed hydrocarbon body while descending into the reaction space 111, and the carbon dioxide supply pipe 113 for injecting carbon dioxide is fixed upward in the body part 110.
  • the upward air flow by the carbon dioxide injected from the carbon dioxide supply pipe 113 acts as a forward vortex (Conventional Vortex Flow) with respect to the discharge direction of the reformed syngas.
  • the air flow by the hydrocarbon body injected from the split feed pipe 152 acts as a reverse vortex (Reverse Vortex Flow) to the discharge direction of the reformed synthesis gas, the reaction space portion 111 by the interaction of each gas flow ) Increases the time that the plasma (P), carbon dioxide, methane and hydrocarbons can be reacted with each other and reformed. The efficiency of reforming is maximized.
  • Reverse Vortex Flow reverse Vortex Flow
  • the inclined surface of the expansion space 170 is formed to protrude upward, the plurality of flame induction blades 171 extending in the outward direction from the center of the body portion 110 are spaced at regular intervals and arranged radially It is preferable to be.
  • the air flow is guided in the direction in which the inner diameter is extended by the flame-induced blade 171 and the plasma flame and each gas flow vortexed by the tangential structures of the carbon dioxide supply pipe 113 and the split supply pipe 152. As it rises, the airflow can be more stably formed.
  • a cylindrical nozzle portion 180 is mounted on the upper end of the body portion 110 to form a stable air flow through the expansion space 170, and induces the discharge of the flame and the modified synthesis gas discharged to the rear end. .
  • the plasma reformer 100 protruding inwardly along the circumference from the upper inner side of the body portion 110 to the By mixing the plasma (P) generated and the injected methane, carbon dioxide, hydrocarbons and the like at a high pressure through the chamber portion 150 to reduce the inner diameter to achieve a pressure change in the reaction space 111 where the reforming reaction occurs
  • the reforming efficiency may be increased, and the plasma P generated in the reaction space 111 may be uniformly mixed with the respective gas streams injected therein, and the combustion flame may be stably maintained.
  • various chemicals are controlled by controlling the hydrogen / carbon monoxide ratio while reducing the amount of electric energy used to generate the plasma (P). Can be generated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention concerne un reformeur à plasma permettant de reformer du méthane (CH4) et du dioxyde de carbone (CO2) injectés à travers un plasma (P) dans un gaz de synthèse contenant, comme composants principaux, de l'hydrogène (H2) et du monoxyde de carbone (CO). Le reformeur à plasma et à micro-ondes selon l'invention comprend : une unité de corps (110) dans laquelle est formée une partie espace réactionnel (111) où le plasma (P) est généré, une conduite d'alimentation en méthane (112) injectant le méthane dans la partie espace réactionnel (111), et une conduite d'alimentation en dioxyde de carbone (113) injectant le dioxyde de carbone dans la partie espace réactionnel (111), lesquelles sont formées respectivement dans la partie espace réactionnel (111) ; une conduite d'évacuation (120) reçue dans la partie espace réactionnel (111) de l'unité de corps (110) et soumise à des micro-ondes ayant une fréquence prédéterminée afin de générer un plasma dans la partie espace réactionnel (111) ; une conduite de guide de lumière (135) raccordée à l'unité de corps (110) de façon à être raccordée à la conduite d'évacuation (120) et qui applique les micro-ondes qui sont transmises à la conduite d'évacuation (120) ; une conduite d'alimentation en corps hydrocarboné (140) disposée dans la partie supérieure de l'unité de corps (110) et introduisant un corps hydrocarboné dans la partie espace réactionnel (111) ; et une partie chambre (150) disposée du côté interne de la partie supérieure de l'unité de corps (110) et formée de façon à se projeter dans la direction du côté interne le long de la circonférence afin de réduire le diamètre interne de la partie espace réactionnel (111).
PCT/KR2013/008657 2012-09-28 2013-09-27 Reformeur à plasma et à micro-ondes WO2014051366A1 (fr)

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WO2020043985A1 (fr) * 2018-08-28 2020-03-05 Europlasma Procédé de production d'un gaz de synthèse par traitement d'un flux gazeux contenant du co2 et un ou plusieurs hydrocarbures
WO2020197703A1 (fr) 2019-03-25 2020-10-01 Recarbon, Inc. Gestion thermique de réacteurs à plasma
WO2020223789A1 (fr) * 2019-05-09 2020-11-12 Pyrogenesis Canada Inc. Production de gaz de synthèse à l'aide de co2 recyclé par reformage combiné à la vapeur et à sec de méthane
WO2022226380A1 (fr) * 2021-04-22 2022-10-27 Bionatus, LLC Systèmes et méthodes de production d'hydrogène et de sous-produits à partir de gaz naturel
EP3948928A4 (fr) * 2019-03-25 2023-01-04 Recarbon, Inc. Systèmes pour commander des réacteurs à plasma

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KR101662646B1 (ko) * 2014-10-31 2016-10-07 한국기초과학지원연구원 스팀플라즈마를 이용한 탄화수소체 개질시스템
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Publication number Priority date Publication date Assignee Title
CN107006112A (zh) * 2014-12-11 2017-08-01 绿色科学有限公司 具备形成有漩涡气流瓦解气体供应部的导波管的等离子体火炬
WO2020043985A1 (fr) * 2018-08-28 2020-03-05 Europlasma Procédé de production d'un gaz de synthèse par traitement d'un flux gazeux contenant du co2 et un ou plusieurs hydrocarbures
FR3085370A1 (fr) * 2018-08-28 2020-03-06 Europlasma Procede de production d'un gaz de synthese par traitement d'un flux gazeux contenant du co2 et un ou plusieurs hydrocarbures
WO2020197703A1 (fr) 2019-03-25 2020-10-01 Recarbon, Inc. Gestion thermique de réacteurs à plasma
EP3948926A4 (fr) * 2019-03-25 2022-12-28 Recarbon, Inc. Réacteur à plasma pour traitement de gaz
EP3948928A4 (fr) * 2019-03-25 2023-01-04 Recarbon, Inc. Systèmes pour commander des réacteurs à plasma
EP3948929A4 (fr) * 2019-03-25 2023-01-11 Recarbon, Inc. Réacteurs à plasma dotés de récupérateurs
EP3948930A4 (fr) * 2019-03-25 2023-01-11 Recarbon, Inc. Gestion thermique de réacteurs à plasma
WO2020223789A1 (fr) * 2019-05-09 2020-11-12 Pyrogenesis Canada Inc. Production de gaz de synthèse à l'aide de co2 recyclé par reformage combiné à la vapeur et à sec de méthane
WO2022226380A1 (fr) * 2021-04-22 2022-10-27 Bionatus, LLC Systèmes et méthodes de production d'hydrogène et de sous-produits à partir de gaz naturel

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