WO2019190244A1 - Système de production de monoxyde de carbone et d'hydrogène à partir de dioxyde de carbone et d'eau au moyen d'un convertisseur réversible d'oxydoréduction et procédé associé - Google Patents

Système de production de monoxyde de carbone et d'hydrogène à partir de dioxyde de carbone et d'eau au moyen d'un convertisseur réversible d'oxydoréduction et procédé associé Download PDF

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WO2019190244A1
WO2019190244A1 PCT/KR2019/003671 KR2019003671W WO2019190244A1 WO 2019190244 A1 WO2019190244 A1 WO 2019190244A1 KR 2019003671 W KR2019003671 W KR 2019003671W WO 2019190244 A1 WO2019190244 A1 WO 2019190244A1
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converter
oxidation
reduction
redox
carbon dioxide
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PCT/KR2019/003671
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Korean (ko)
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김석기
전기원
곽근재
박해구
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한국화학연구원
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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
    • 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
    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • 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
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • 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
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to a system and a method for producing carbon monoxide and hydrogen from carbon dioxide and water using a reversible redox converter, and more particularly, to a reversible redox converter through plasma Producing carbon monoxide (CO), hydrogen (H 2 ) and the like by contacting the oxygen-reversible reversible redox converter with a gas containing at least one of carbon dioxide (CO 2 ), water vapor (H 2 0)
  • CO carbon monoxide
  • H 2 hydrogen
  • a system and method thereof are provided.
  • thermochemical redox cycle As an alternative to solving the viable environment and energy problem. Attention has been paid to techniques for producing and producing hydrocarbon energy from and hydrogen.
  • thermochemical redox cycle refers to a process at high temperatures, and the technology using solar energy as such a high temperature energy source is actively being researched and developed.
  • thermochemical redox cycle of solar heat uses two separate reduction / oxidation reactions using metal oxides (hereinafter referred to as 'reversible redox conversion agents') that can reversibly generate and heal oxygen defects as a reaction medium. Takes place in stages. Here, in the first stage of reversible oxidation, the reversible redox converter is reduced at high temperatures by the concentrated solar energy (generally> 1473 K), and in the next step the reversible redox converter is reduced in contact with carbon dioxide and / or water vapor. Produces carbon monoxide and hydrogen. The resulting syngas mixture is converted to replaceable hydrocarbons (gasoline, diesel, kerosene, etc.) using industrially recognized catalysts such as FiscHer-TropscH synthesis.
  • 'reversible redox conversion agents' metal oxides
  • thermochemical redox cycle is as follows.
  • Stage 1 Concentrated solar energy is used as a heat source, and the reversible redox convertor loses oxygen and becomes partially deficient in oxygen, and the removed oxygen is produced in the form of molecular oxygen. )
  • Step 2 (oxidation step): The reversible redox converter is supplied with carbon dioxide (CO 2 ) and water vapor (H 2 0) to the reversible redox converter in the oxygen-deficient state generated in step 1 CO 2 ) and water vapor (H 2 O) are obtained and oxidized to produce carbon monoxide (CO) and hydrogen (H 2 ) (2a, 2b), and the reversible redox converter is returned to its original state.
  • CO 2 carbon dioxide
  • H 2 0 water vapor
  • H 2 O water vapor
  • the redox converting agent returned to the original state is reduced again through the first step and reoxidized in the second step.
  • thermochemical redox cycle using the concentrated solar energy as described above can achieve high solar energy conversion efficiency and use eco-friendly renewable energy, but the solar thermal collection to supply the high temperature required for the thermochemical redox cycle There was a problem that the space and cost was too great to build a facility.
  • the present invention provides a new system for producing carbon monoxide and hydrogen from carbon dioxide (CO 2 ) and water vapor (H 2 0) through a thermochemical redox cycle using plasma without using solar energy. I would like to present.
  • the present invention solves the problem of power supply and demand that can occur by using a floating power including surplus power, surplus power at night, and renewable energy generated by over-producing the power used to generate such plasma in the power plant as a power source I would like to.
  • the frequency is changed in order to return the changed frequency generated by the mismatch between the demand power and the supply power to the standard frequency. Adjust your power to respond.
  • the standard frequency of Korean power system is specified as 60Hz. If the power demand increases and the power supply is insufficient, the frequency drops below 60 Hz, so the power is raised at the power plant and the frequency is adjusted.
  • the frequency has been adjusted through the following operation method, in the frequency following operation method, the operation cost is high and the generator efficiency is different for each power plant, so that the efficiency of the power plant is poor when adjusting the output, resulting in a decrease in the actual supply capacity. There is a problem that the failure rate of power plant equipment is increased.
  • the present invention is a method for solving such a problem, the flow power generated by the mismatch of the power supply and the demand power, such as surplus power generated by over-produced in the power plant, surplus power at night and renewable power including renewable energy
  • the in the plasma generating apparatus while receiving power at a lower cost than the general power, it is possible to solve the above problems caused by the mismatch between the power demand and the power supply in the power plant.
  • Korean Patent Publication No. 10-2018-0004165 (published 2018-01-10) relates to a method for converting carbon dioxide (CO 2 ) to a synthesis gas, and more particularly, to a solid-supported catalyst including Cu and Mn.
  • the prior art is a technique for preparing carbon monoxide (CO) by reacting hydrogen and carbon dioxide (CO 2 ) in the presence of a catalyst, and does not include hydrogen, but rather includes a technique of using plasma as a heat source required for the reaction. not.
  • Patent Publication No. 10-1768001 (August 08, 2017) relates to a hybrid solar-chemical circulation process using oxygen donor particles, and more specifically, to supply a high temperature heat to the reduction reactor through a solar collector, The hydrocarbon fuel and the oxygen donor particles are supplied to the reduction reactor so that the hydrocarbon fuel is converted into the synthesis gas by a partial oxidation reaction by the oxygen donor particles, the oxygen donor particles are reduced, and then the reduced oxygen donor particles are transferred to the oxidation reactor.
  • a technique for generating hydrogen (H 2 ) by a reduction reaction with steam is described. Since the prior art Patent Publication No.
  • 10-1768001 uses a reducing gas to reduce oxygen donor particles (reversible redox conversion agent in the present invention), a problem of releasing greenhouse gases such as carbon dioxide (CO 2 ), nitrogen oxides, etc.
  • oxygen donor particles reversible redox conversion agent in the present invention
  • CO 2 carbon dioxide
  • nitrogen oxides etc.
  • Japanese Laid-Open Patent Publication JP 2003-027241 (published Jan. 29, 2003) generates microwave plasma at a low pressure from a raw material gas composed of carbon dioxide (CO 2 ), hydrogen (H 2 ) and / or water vapor (H 2 0).
  • the Japanese Laid-Open Patent Publication JP 2003-027241 is a technique for converting carbon dioxide (CO 2 ) using plasma, but is different from the present invention using a reversible redox converter.
  • the present invention is to provide a system having a higher efficiency in the system for producing carbon monoxide (CO) and hydrogen (H 2 ) by taking oxygen from carbon dioxide (CO 2 ) and water vapor (H 2 0) and the like. There is this.
  • the present invention is a system that can ensure the efficient use of the flow power by making it possible to use the flow power, such as surplus power generated by overproduction in the power plant, surplus power at night and irregularly generated renewable energy as a useful energy source And to provide a method thereof.
  • a system for producing a product gas containing at least one of carbon monoxide, hydrogen from a source gas containing at least one of carbon dioxide and water vapor using a reversible redox conversion agent as an embodiment
  • a redox conversion reactor having a space formed therein so as to be filled with a reversible redox converter;
  • a plasma generator capable of generating a plasma in an internal space of the oxidation-reduction conversion reactor;
  • a gas discharge unit configured to discharge the gas containing at least one of carbon monoxide and hydrogen in the acid reduction-reduction conversion reactor to the outside. Characterized in that it comprises a.
  • the system uses the heat of the high-temperature exhaust gas discharged to the outside of the oxidation-reduction conversion reactor in the reduction process of the reversible redox conversion agent, the inside of the oxidation-reduction conversion reactor in the oxidation process And a heat exchanger for heating carbon dioxide (CO 2 ) and / or water vapor (H 2 0) supplied to the apparatus.
  • CO 2 carbon dioxide
  • H 2 0 water vapor
  • the inert gas is supplied into the oxidation-reduction conversion reactor, and the lattice oxygen released while the reversible oxidation-reduction converter in the oxidation state is reduced is oxygen gas.
  • a gas containing at least one of carbon dioxide (CO 2 ), water vapor (H 2 0) is supplied into the oxidation-reduction conversion reactor,
  • oxygen is desorbed from at least one of carbon dioxide (CO 2 ) and water vapor (H 2 0) to produce at least one of carbon monoxide (CO) and hydrogen (H 2 ), and through the plasma generator
  • CO carbon dioxide
  • H 2 0 water vapor
  • CO carbon monoxide
  • H 2 hydrogen
  • the plasma generating device is driven by the flow power
  • the flow power is characterized in that it includes surplus power, excess power generated at night and renewable energy and renewable energy generated in the power plant.
  • the reversible redox converter is a metal oxide having a fluorspar structure; Metal oxides having a spinel structure; Oxides having a perovskite structure represented by general formula ABO 3 (A and B are metal elements); Oxides having a brown miralite structure represented by general formula A 2 B 2 O 5 (A and B are metal elements); At least one selected from AlOx, MnOx, FeOx, CoOx, NiOx, CrOx, BiOx, GaOx, BOx, LaOx, CeOx is used.
  • the redox conversion reactor is provided with at least one, characterized in that both the reduction process and the oxidation process of the reversible redox conversion agent in each of the redox conversion reactor.
  • the redox conversion reactor is provided with at least two, the reduction process and the oxidation process of the reversible redox converter is characterized in that each performed in a separate redox conversion reactor.
  • the reversible oxidation-reduction converter of the present invention a method for producing a product gas containing one or more of carbon monoxide, hydrogen from a source gas containing one or more of carbon dioxide, water vapor, (1) internal Inert gas is supplied into an oxidation-reduction conversion reactor filled with a reversible oxidation-reduction converter in an oxidation state in a space, and thermal energy is supplied using a plasma to reduce the reversible oxidation-reduction converter in the oxidation state, and the reversible A first step of allowing the lattice oxygen released from the redox conversion agent to be discharged as a gas; And (2) supplying one or more of carbon dioxide (CO 2 ) and water vapor (H 2 0) to a space filled with a reversible redox converter in a reduced state after the first step, thereby oxidizing the reversible redox converter. Characterized in that it comprises a second step of taking oxygen from one or more of carbon dioxide (CO 2
  • the method uses a high temperature exhaust gas heat discharged to the outside of the redox conversion reactor in the first step, to heat the feed supplied into the redox conversion reactor of the second step. It is characterized by.
  • the method is characterized in that the plasma generation in the first step is driven by at least one of the surplus power generated by the excess production in the power plant, the surplus power at night and the renewable energy.
  • the temperature of the reduction step of the reversible redox converter is 1000 °C to 2000 °C
  • the temperature of the oxidation step of the reversible redox converter is characterized in that 500 °C to 1400 °C do.
  • the method comprises a synthesis gas comprising carbon monoxide (CO) and hydrogen (H 2 ) produced in the oxidation step of the reversible redox converter using a FiscHer-TropscH reaction.
  • the present invention uses a redox process to take oxygen from carbon dioxide (CO 2 ), water (H 2 0) and the like to produce carbon monoxide (CO) and hydrogen (H 2 ), etc.
  • CO carbon dioxide
  • H 2 0 water
  • the plasma as a heat source
  • the efficiency of the process of manufacturing carbon monoxide (CO), hydrogen (H 2 ), etc. from (CO 2 ), water (H 2 0), etc. can be improved.
  • the present invention can be used immediately when the flow power occurs, the surplus power generated by the excess production in the power plant, the surplus power at night and the discontinuously produced renewable energy can be used as an energy source, the power generation is applied to the power plant
  • the power generation is applied to the power plant
  • FIG. 1 shows a system for converting carbon dioxide (CO 2 ) and water vapor (H 2 0) using a reversible redox converter according to an embodiment of the present invention.
  • FIG. 2 illustrates a system for converting carbon dioxide (CO 2 ) and water vapor (H 2 0) using a reversible redox converter further comprising a heat exchanger according to an embodiment of the present invention.
  • FIG. 3 illustrates a redox conversion reactor in a system for converting carbon dioxide (CO 2 ) and water vapor (H 2 0) using a reversible redox converter according to an embodiment of the present invention.
  • Figure 4 is a graph measuring the oxygen generation amount of the ceria sample by the external heating in the process of reduction of the reversible redox conversion using a thermogravimetric analyzer (TGA).
  • TGA thermogravimetric analyzer
  • FIG. 5 is a graph showing the amount of oxygen generated in a ceria sample by plasma during the reduction of the reversible redox conversion agent.
  • the present invention supplies heat required for the oxidation and reduction reaction using a plasma generator, and in the oxidation process of the reversible redox converter, the reversible redox converter is carbon dioxide (CO 2 ) and / or water vapor (H 2 0). Oxygen is deprived of oxygen to produce carbon monoxide (CO) and hydrogen (H 2 ), and in the reduction process of the reversible oxidation-reduction converter, the lattice oxygen is removed from the reversible oxidation-reduction converter in the oxidation state, thereby reversing the oxygen-deficient state.
  • a system for producing redox converters is disclosed.
  • the reversible redox converter has both oxygen ion conductivity and includes both metal / nonmetal oxides which may have reversible oxygen deficiencies. As described above, the reversible redox converter reacts with carbon dioxide (CO 2 ) and / or water vapor (H 2 O) to accept oxygen and oxidizes itself, and in the reduction process, oxygen in the lattice escapes due to high thermal energy. It is different from the catalyst because it is directly involved in the reaction process such as reduction.
  • Non-limiting examples of the reversible redox converter include cerium oxide; Metal oxides having a fluorspar structure represented by stabilized zirconia and the like; Metal oxides having a spinel structure; Oxides having a perovskite structure represented by general formula ABO 3 (A and B are metal elements); Oxides having a brown miralite structure represented by general formula A 2 B 2 O 5 (A and B are metal elements); At least one selected from AlOx, MnOx, FeOx, CoOx, NiOx, CrOx, BiOx, GaOx, BOx, LaOx, CeOx may be used.
  • the reversible redox converter in the oxidation state is MO ox
  • the reversible redox converter in the reduced state is represented by MO red . That is, the redox process in the present invention uses a redox pair (MO ox / MO red ) of a reversible redox converter as a reaction medium.
  • a system for preparing syngas from carbon dioxide using the reversible redox converter of the present invention includes a redox converter 110, 110 ′, a plasma generator 120, The gas inlet 130, 130 ′, the gas outlet 140, 140 ′, and the power supply 150 are configured.
  • the redox conversion reactors 110 and 110 have an internal space formed therein and a reversible redox converter filled in the internal space.
  • the plasma generator 120 is a device capable of generating a plasma inside the redox conversion reactor.
  • plasma is classified into a high temperature plasma (balanced plasma) and a low temperature plasma (non-equilibrium plasma).
  • the high temperature plasma is a plasma that induces a high temperature of 1000 ° C. or more.
  • an oxygen deficiency state is formed in a reversible redox converter.
  • the high temperature plasma is required because the step requires high temperature.
  • High-temperature thermal plasma generator using electrical energy can be defined as a device that converts a large amount of thermal energy that can be used for melting and reducing the object.
  • High temperature thermal plasma generation must be supplied with sufficient energy for gas ionization. This energy can be generated as, but not limited to, an electric arc occurring at two electrodes. Passing the gas between hot arcs allows for a transition to a gas plasma.
  • the apparatus for generating plasma by such a process is called an arc plasma generator or a direct current plasma method and is the most widely used method.
  • plasma generation is possible through a strong electric field, and there are capacitive plasmas using an annular electrode installed outside the discharge tube, and inductive plasmas using a high frequency electromagnetic field induced by a cylindrical induction coil. .
  • the gas inlet 130, 130 ′ supplies inert gas, carbon dioxide (CO 2 ), and water vapor (H 2 O) to the internal space of the redox conversion reactor.
  • the gas inlet may selectively supply inert gas, carbon dioxide (CO 2 ), and water vapor (H 2 O) into the reactor through a gas inlet control device such as a valve.
  • the gas discharge unit (140, 140 ') is to discharge the gas inside the conversion-reduction conversion reactor to the outside.
  • the system for converting carbon dioxide using the reversible redox converter of the present invention the redox conversion reactor (110, 110 '), the plasma generator 120, the gas inlet (130, 130')
  • a heating device 121 and / or a controller may be additionally included.
  • the power supply unit 150 is the oxidation-reduction conversion reactor (110, 110 '), plasma generator 120, heating device 121, gas inlet 130, 130', gas outlet 140 140 '), power to a control unit (not shown).
  • a part of the lattice oxygen of the reversible redox converter is removed by transferring high temperature heat to the reversible redox converter using a high temperature plasma, and the reversible oxidation -The reducing converter is converted to a state in which oxygen is deficient, and becomes a state which is easy to receive oxygen from the outside.
  • the reversible oxidation of the oxygen-deficient state by supplying a gas containing at least one of carbon dioxide (CO 2 ), water vapor (H 2 0) into the oxidation-reduction conversion reactor
  • the reducing converter accepts oxygen from at least one of carbon dioxide (CO 2 ) and water vapor (H 2 0) to fill the depleted oxygen, which is converted to carbon monoxide (CO) and hydrogen (H 2 ), respectively.
  • Step 1 Reduction of the reversible redox converter
  • the inert gas is supplied without supplying a separate reducing reactant, and the inert gas is converted into plasma through a plasma generator.
  • a high temperature heat is required in the reduction process of the reversible redox converter, and a temperature of at least 1000 ° C. or more is preferable. Is 1200 ° C or higher, more preferably 1600 ° C or higher.
  • the inert gas may be one or a mixture of two or more selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn), nitrogen, and the like. It can be used as an efficient plasma generator gas.
  • the reversible redox converting agent which is deficient in oxygen, generated in the first step, is in a state of easily accepting oxygen, and the oxygen is absorbed at a relatively low temperature even from stable molecules carbon dioxide (CO 2 ) and water vapor (H 2 0). It becomes acceptable. Therefore, the temperature in the second step can be performed even at a temperature much lower than the temperature of the first step.
  • thermal energy is mainly transferred from the outside to heat not only a reversible redox converter but also peripheral devices such as a conversion reactor supporting the reversible redox converter. Since it requires a lot of energy required for heating, the process time for heating is also long, there was a disadvantage that takes a lot of time for the reduction reaction.
  • the heating rate is suitably 50 to 1000 °C per minute, preferably 100 to 500 °C per minute.
  • a carbon monoxide (CO) and hydrogen (H 2 ) are produced by contacting the reversible redox conversion agent in a reduced state with a gas containing at least one of carbon dioxide (CO 2 ) and (H 2 0) ( Second step: oxidation of the reversible redox converter).
  • the heating in the second step may use the exhaust gas heat in the first step.
  • the system of the present invention may further include a heat exchanger 160.
  • the inert gas containing the oxygen gas discharged to the outside in the first step is very high temperature, while the carbon dioxide (CO 2 ) and water vapor (H 2 0), the feed gas in the second step is required for the reaction at low temperature Since the temperature must be heated to a temperature, the exhaust gas of the first stage and the feed gas of the second stage may be subjected to heat exchange through the heat exchanger, thereby increasing the temperature of the feed gas of the second stage.
  • the heat exchanger may be configured in one or more of a shell & tube heat exchanger, a double pipe type heat exchanger, a plate type heat exchanger, or a coil type heat exchanger. .
  • the second stage Since the required reaction temperature in the second stage is much lower than that of the first stage, if the gas flow rates in the second stage and the first stage are properly adjusted, the second stage merely uses waste heat of the exhaust gas of the first stage. Also, the heat required for the reaction can be supplied to avoid the heat energy supply from the outside.
  • the heat energy when the heat energy is insufficient only by the use of the waste heat, the heat energy may be additionally supplied by external heating or plasma.
  • the temperature during the reduction process of the reversible redox converter, which is the first step is 1000 ° C to 2000 ° C, and the reversible redox conversion, which is the second step, is performed.
  • the temperature at the time of the oxidation process of agent is 500 to 1400 degreeC.
  • the temperature of the first step is set to 1400 ° C to 1800 ° C
  • the temperature of the reversible oxidation-reduction converter during the oxidation step is set to 900 ° C to 1400 ° C.
  • the temperature at the time of the reduction process is less than 1000 ° C it is difficult to reduce, if the temperature exceeds 2000 ° C the efficiency of thermal energy is lowered.
  • the temperature during the oxidation process is 500 ° C or less, or 1400 ° C or more, the oxidation reaction may be difficult to occur.
  • the system using the plasma according to the present invention uses the flowing power (Fluctuating power) as the energy source of the plasma generating apparatus.
  • the floating power may be, for example, surplus power produced in excess of demand power in a power plant such as a thermal power plant or a nuclear power plant, or may be renewable energy such as unstable supply of solar energy and wind energy.
  • a thermal power plant such as a thermal power plant or a nuclear power plant
  • the use of surplus power produced in a thermal power plant is good because it can directly use carbon dioxide (CO 2 ), which is essential in thermal power generation, as a feedstock for the reforming reaction.
  • CO 2 carbon dioxide
  • the reduction process and the oxidation process of the reversible redox converter is carried out in one redox conversion reactor
  • the reduction process and the oxidation process of the reversible oxidation-reduction converter may be performed in separate oxidation-reduction conversion reactors, respectively. That is, the reduction process of the reversible redox converter is performed in the first redox conversion reactor 110, and the oxidation process of the reversible redox converter is performed in the second redox conversion reactor 110 '. It can also be done in.
  • the reversible redox conversion agent in the reduced state in the first redox conversion reactor 110 Is supplied to the second redox conversion reactor 110 ′, and a reversible redox conversion agent in an oxidation state in the second redox conversion reactor is supplied to the first redox conversion reactor to redox.
  • the converting agent may be moved, and a method of converting the gas to be supplied may be used depending on the oxidation and reduction states of the oxidation-reducing converter.
  • the type of the redox conversion reactor of the present invention is a fixed bed, a fluidized bed or a moving bed, or an entrained flow bed in which a reversible redox conversion agent is accompanied by a gas flow. ) And the like.
  • system using the reversible redox converter according to the present invention further comprises a Fischer-TropscH reactor, produced in the redox conversion reactor using the Fischer-Tropsch reactor.
  • Hydrocarbon (gasoline, diesel, kerosene, etc.) fuel may be produced from the syngas.
  • Oxygen in the analyzer chamber gradually decreased after Ar gas was introduced due to Ar inflow, and then oxygen was not measured at all after about 140 minutes. After that, oxygen was not measured at all after heating up to 1600 ° C. This confirmed that there was no oxygen generation source in the analyzer.
  • 114.9 mg of ceria powder was prepared in the analyzer of Comparative Example 1-1, and Ar (120 cc / min) was added in the same manner as in Comparative Example 1-1. It was confirmed that oxygen was not measured at 140 minutes after flowing Ar as in Comparative Example 1-1.
  • the temperature increase step is as shown in Figure 4 and the temperature increase rate was 10 °C / min was maintained at 1600 °C to maintain for 1 hour.
  • Oxygen meter (Jedis, ZR-5) was used to quantify oxygen released from ceria. As shown in FIG. 4, it was confirmed that oxygen was measured from the measurement point 240 minutes (1200 ° C.), which is oxygen generated from ceria, and the amount of the generated oxygen was quantified.
  • the time required for oxygen generation means the time from when oxygen starts to occur in ceria until no more lattice oxygen is released.
  • the mass of oxygen generated was 5.337 mg. It was 5.9% of the theoretical value in mg, and the time to remove all the oxygen was about 23.5 minutes.
  • the chamber temperature inside the plasma was instantaneously increased so that it was not possible to maintain a constant temperature increase rate, but it was confirmed that the temperature was raised to 1600 ° C. within 5 minutes.
  • the amount of oxygen generated is shown in Table 2, about 7.1% of oxygen was produced compared to the theoretical amount of oxygen, and the duration of oxygen generation was 0.53 minutes.
  • Example 1 and Comparative Example 1-2 the plasma temperature is higher than that of a general heating device (thermogravimetric analyzer), so that the oxygen is depleted by removing lattice oxygen from the reversible redox converter. It can be seen that the time required for the conversion to the converted state is much shorter, and also the reduction degree of the acid reduction-reduction converter is higher, and the time required for oxygen generation is greatly reduced. As a result, it can be confirmed that the oxidation-reduction conversion reaction can be performed more efficiently in a very quick time than in the case of using a plasma when using a plasma.
  • a general heating device thermogravimetric analyzer
  • thermogravimetric analyzer (Setaram Instrumntation, SETSYS Evolution TGA) was maintained at 900 ° C without the ceria in order to confirm the possibility of thermal decomposition due to the temperature of the steam, and the temperature of steam and Ar was set to 900 ° C. 50 cc / min each. In order to quantify the amount of hydrogen generated, gas chromatography (Younglin Instruments, YL 6100) was used. The experiment confirmed that no hydrogen was generated.
  • the amount of hydrogen generated was quantified by supplying steam to ceria lacking lattice oxygen produced under the conditions of Comparative Example 1-2 in Experimental Example 1.
  • the steam and Ar were set at 900 ° C. and fed at 50 cc / min, respectively.
  • the results shown in Table 3 were obtained, and the ratio of hydrogen produced to oxygen deficient was 81%.
  • the ratio of hydrogen produced relative to the deficient oxygen was calculated using the theoretical value (theoretical hydrogen generation volume) of the hydrogen volume generated when all the deficient oxygen of ceria was filled.
  • the amount of hydrogen generated was quantified by supplying steam to ceria deficient in lattice oxygen under the conditions of Example 1 in Experimental Example 1.
  • the temperature of steam and Ar was set at 900 ° C. and fed at 12 L / min, respectively.
  • gas chromatography Youngnglin Instruments Co., Ltd., YL 6100 was used, and the results shown in Table 4 were obtained. It was confirmed that the molar ratio of hydrogen produced relative to the amount of oxygen deficient was 85%.
  • Example 2 Compared with Comparative Example 2-2 and Example 2, the hydrogen generation of Example 2 according to the present invention is higher, which is the reduction degree of the redox conversion agent reduced by using the plasma according to the present invention. It is presumably because it is higher, so that the decomposition of water is better.
  • thermogravimetric analyzer (Setaram Instrumntation Co., Ltd., SETSYS Evolution TGA) was maintained at 900 °C, CO 2 and Ar temperature was set to 900 °C were supplied at 50 cc / min each.
  • gas chromatography Youngnglin Instruments, Inc., YL 6100 was used. Experiments confirmed that no carbon monoxide was generated.
  • the amount of carbon monoxide produced by supplying carbon dioxide to ceria lacking lattice oxygen under the conditions of Comparative Example 1-2 was quantified.
  • the temperature of carbon dioxide and Ar was set at 900 ° C. and fed at 50 cc / min.
  • gas chromatography Youngnglin Instruments Co., Ltd., YL 6100 was used, and the results are shown in Table 5. It was confirmed that the molar ratio of carbon monoxide produced relative to the amount of oxygen deficient was 89%.
  • the ratio of the produced CO to the deficient oxygen was calculated using the theoretical value (theoretical CO generating volume) of the CO volume generated when all the deficient oxygen of the ceria was filled.
  • the amount of carbon monoxide generated by supplying carbon dioxide to lattice oxygen deficient ceria under the conditions of Example 1 in Experimental Example 1 was quantified.
  • the temperature of carbon dioxide and Ar was set at 900 ° C. and fed at 12 L / min, respectively.
  • gas chromatography Youngnglin Instruments, Inc., YL 6100 was used. The results as shown in Table 6 were obtained, and the molar ratio of carbon monoxide produced relative to the amount of deficient oxygen was found to be 90%.
  • Example 3 Compared with Comparative Example 3-2 and Example 3, the generation of carbon monoxide of Example 3 according to the present invention appears higher, which is the reduction degree of the oxidation-reduction converter reduced by using the plasma according to the present invention It is believed to be higher because it decomposes carbon monoxide better.

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Abstract

La présente invention concerne un système de production de gaz synthétique à partir de dioxyde de carbone à l'aide d'un convertisseur réversible d'oxydoréduction et un procédé associé. Plus spécifiquement, l'invention concerne un système de production de monoxyde de carbone et d'hydrogène à partir de dioxyde de carbone et d'eau à l'aide d'un convertisseur d'oxydo-réduction réversible et un procédé associé. Dans ledit procédé un gaz source contenant au moins l'un parmi le dioxyde de carbone (CO2) et la vapeur (H20) est introduit dans un réacteur de conversion d'oxydoréduction chargé avec un convertisseur d'oxydoréduction réversible dans un état de réduction et la chaleur générée à travers un générateur de plasma est introduite dans celui-ci, de sorte que l'oxyde métallique dans un état de réduction soit oxydé en vapeur d'oxygène à partir de dioxyde de carbone (CO2) et en vapeur (H20) pour produire du monoxyde de carbone (CO) et de l'hydrogène (H2); et un gaz inerte est introduit dans le réacteur d'oxydoréduction chargé avec le convertisseur d'oxydoréduction réversible dans un état d'oxydation, et un plasma est utilisé pour réduire le convertisseur d'oxydoréduction réversible dans un état d'oxydation.
PCT/KR2019/003671 2018-03-30 2019-03-28 Système de production de monoxyde de carbone et d'hydrogène à partir de dioxyde de carbone et d'eau au moyen d'un convertisseur réversible d'oxydoréduction et procédé associé WO2019190244A1 (fr)

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KR102621148B1 (ko) * 2021-11-11 2024-01-04 이화여자대학교 산학협력단 바이오매스 가스화 공정과 결합된 수소 생성 열화학적 레독스 사이클

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