CN107804824B - Composite calcium-iron oxygen carrier and chemical-looping hydrogen production synergistic CO thereof2Trapping method - Google Patents
Composite calcium-iron oxygen carrier and chemical-looping hydrogen production synergistic CO thereof2Trapping method Download PDFInfo
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Abstract
The invention discloses a composite calcium-iron oxygen carrier and a chemical chain hydrogen production synergistic CO thereof2Trapping method of Ca2Fe2O5As a chemical-looping hydrogen production oxygen carrier, the compound calcium-iron oxygen carrier can realize chemical-looping hydrogen production by two-step oxidation-reduction reaction and is cooperated with CO2And (3) gas capture, wherein the corresponding reactor can realize chemical looping hydrogen production only by a fuel reactor and a steam reactor. Fuel reduction stage, Ca2Fe2O5Is reduced to generate simple substance Fe and CaO, can separate and capture CO simultaneously2A gas; in the steam oxidation stage, simple substances Fe and CaO react with steam to generate Ca in one step2Fe2O5And high-purity hydrogen is obtained, and the two-step chemical-looping hydrogen production cycle based on the novel calcium-iron oxygen carrier can be completed by the circulation. The oxygen carrier can be prepared from Fe in one step in the circulating process0Is oxidized into Fe3+With conventional Fe2O3More hydrogen can be generated than if the molar amount of iron is the same as the oxygen carrier. Meanwhile, the chemical-looping hydrogen production method has great advantages in the aspects of wear resistance, energy consumption and the like of the oxygen carrier.
Description
Technical Field
The invention relates to a composite calcium-iron oxygen carrier and a chemical chain hydrogen production synergistic CO thereof2A trapping method belongs to the technical field of combustion chemical industry.
Background
The chemical looping combustion technology is that traditional fuel is directly combusted with air or oxygen, the oxygen is transferred to the fuel by the oxygen carrier to be combusted under the condition that the fuel and the air are not in contact by virtue of the oxidation and reduction of the oxygen carrier in two reactors. As a novel energy utilization form and technology, the chemical looping combustion has the advantages of high fuel conversion rate, carbon dioxide separation and capture, low pollutant emission and the like. The chemical looping hydrogen production technology is an efficient and environment-friendly hydrogen production mode based on chemical looping combustion. Compared with the technology, the traditional steam reforming technology has lower energy conversion efficiency and needs to consume fossilEnergy sources and technical routes thereof are complicated. By adopting the chemical chain hydrogen production technology, not only can high-purity hydrogen be prepared, but also the separation in the system and the capture of CO can be realized2A gas.
The hydrogen energy is used as a clean and efficient secondary energy source, the combustion efficiency is high, and the product is clean and pollution-free. The hydrogen energy has wide application range and plays an irreplaceable role in various social industries such as energy, electric power, chemical synthesis and the like. The traditional chemical chain hydrogen production technology consists of a fuel reactor, a steam reactor and an air reactor, and Fe2O3Or modified Fe2O3As oxygen carrier, the oxygen carrier is reduced into Fe or FeO through a fuel reactor, and the oxygen carrier is oxidized into Fe through a steam reactor3O4And the air reactor is further oxidized to Fe2O3Thereby realizing three-step reduction and oxidation of the iron-based oxygen carrier and the synergy of chemical chain hydrogen production and CO under the iron-based oxygen carrier2And (4) trapping. In the chemical looping hydrogen production process, the oxygen carrier is oxidized and reduced in three reactors, namely a steam reactor, a fuel reactor and an air reactor, so that CO is captured while high-concentration hydrogen is prepared2A gas. As a carrier of oxygen and energy, the use of a high-performance oxygen carrier is the core of the chemical-looping hydrogen production technology. Researchers at home and abroad have studied the performance of metal oxides such as Ni, Cu, Fe, Mn and the like as oxygen carriers, and the thermodynamic property and the sintering resistance of the metal oxides, and the iron-based oxygen carrier has obvious advantages compared with other oxygen carriers.
However, single iron oxide is used as an oxygen carrier, and the hydrogen production by oxidation reduction for multiple times has poor circulation stability, so that serious surface sintering and pore blocking occur, and the hydrogen production effect is seriously influenced. In the steam gasification stage, Fe can be oxidized to Fe only by steam from zero valence3O4In this state, the combustion stage is required to return Fe to Fe3+Status. Making Fe by different preparation methods such as impregnation, coprecipitation, ion exchange and sol-gel2O3With other inert carriers, e.g. Al2O3、ZrO2、TiO2、CeO2、MgAl2O4And the like, and can improve the activity or stability of the oxygen carrier to a certain extent, but does not improve the oxidation degree of Fe in the process of oxidizing Fe by water vapor. Based on the research, the oxygen carrier for the novel chemical-looping hydrogen production with low cost and high efficiency is provided, and is the key for the development of the chemical-looping hydrogen production technology.
Disclosure of Invention
The technical problem is as follows: the invention provides a composite calcium-iron oxygen carrier and a chemical chain hydrogen production synergistic CO thereof2The trapping method comprises extracting Ca2Fe2O5As an oxygen carrier for chemical looping hydrogen production, the method can replace the traditional three-step chemical looping hydrogen production, the chemical looping hydrogen production can be realized through two steps of fuel reduction and steam gasification, and CO is captured at the same time2A gas. The oxygen carrier has good cycle stability, high valence utilization rate of iron, and greatly reduced reaction abrasion of the oxygen carrier in the circulation of the fluidized bed.
The technical scheme is as follows: the composite calcium-iron oxygen carrier and the chemical chain hydrogen production thereof cooperate with CO2A trapping method comprising the steps of:
1) using Ca2Fe2O5As oxygen carrier, CO and CH are added4And any one of the synthesis gas is taken as a reducing agent, oxygen carrier reduction reaction is carried out in a fuel reactor at 850-950 ℃, Fe and CaO states are obtained by reduction, and CO generated by the oxygen carrier reduction reaction is collected2；
2) Feeding the reduced Fe and CaO into a steam reactor as an oxygen carrier, and carrying out an oxygen carrier oxidation reaction with water vapor as an oxidant at the temperature of 850-950 ℃ to obtain Ca2Fe2O5Simultaneously trapping high-concentration hydrogen generated by the oxidation reaction of the oxygen carrier and obtaining Ca2Fe2O5And returned to the fuel reactor.
In a preferred embodiment of the method of the present invention, the synthesis gas in step 1) is CO or H2、CH4And CO2A mixture of two or more of them.
In a preferred embodiment of the process according to the invention, the synthesis gas in step 1) isAny of the following: the gas generated by coal gasification, the gas generated by coal pyrolysis, the gas generated by biomass gasification and the gas generated by biomass pyrolysis, wherein the main components of the gas comprise H2、CO、CH4And CO2。
In a preferred embodiment of the process of the invention, both the fuel reactor and the steam reactor are fluidized bed reactors.
The chemical chain hydrogen production is cooperated with CO2In a preferred embodiment of the trapping method, the fuel reactor and the steam reactor used in the steps 1) and 2) are fluidized bed reactors.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1) the invention proposes to use Ca2Fe2O5As an oxygen carrier for chemical looping hydrogen production, the oxygen carrier is used for the chemical looping hydrogen production in cooperation with CO2And (4) trapping. Ca2Fe2O5During the reduction process of the oxygen carrier, the intermediate valence state is not changed, and the oxygen carrier can be directly reduced into CaO and Fe. And a large amount of carbon deposition in the reduction process is avoided while the reduction rate is ensured.
2)Ca2Fe2O5The catalyst is used as an oxygen carrier for chemical-looping hydrogen production or chemical-looping combustion, has better oxygen carrying capacity, and can be used for producing CO or CH4As the reducing agent, the carbon deposit has better stability, and the carbon deposit amount is less and the circulation stability is stronger in the reduction stage adopting CO as the reducing agent. The oxygen carrier has stable conversion rate and strong reactivity in the oxidation-reduction stage, and is a prospect oxygen carrier of a two-step chemical-looping hydrogen production technology.
3) The method of the invention adopts Ca2Fe2O5As a chemical chain hydrogen production oxygen carrier, and conventional Fe2O3Fe as compared with its modified oxygen carrier0Can be oxidized into Fe in one step3+Therefore, an air reactor in the traditional chemical looping hydrogen production can be omitted. The oxygen carrier can realize the chemical looping hydrogen production and the CO coordination only by two steps of reduction of the fuel reactor and oxidation of the steam reactor2Trapping, and producing hydrogen under the condition that the hydrogen production amount is equal to the mole number of iron and is completely reduced in the reduction stageThe amount can be increased by 12.5%. And because an air reactor is saved, the cost of the chemical looping hydrogen production process is greatly reduced, the abrasion degree of the oxygen carriers in the reactor is also greatly reduced with the same cycle number, and the energy loss of the whole reaction cycle can be reduced by reducing the reactor.
Drawings
FIG. 1 shows Ca2Fe2O5Catalyst H2-TPR experimental results;
FIG. 2 shows different oxygen carriers (Ca) with CO as a reducing agent2Fe2O5With Fe2O3) Comparing the reduced performance;
FIG. 3 shows XRD experimental results of oxygen carriers at different reduction times;
FIG. 4 shows the different concentrations of CO (5%, 10%, 20%, 30%) versus Ca with CO as a reducing agent2Fe2O5The influence of the reduction stage of the oxygen carrier;
FIG. 5 shows the temperature difference (800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C) of CO as a reducing agent versus Ca2Fe2O5The influence of the reduction stage of the oxygen carrier;
FIG. 6 is CH4Different oxygen carriers (Ca) as reducing agents2Fe2O5With Fe2O3) Comparing the reduced performance;
FIG. 7 shows different reductants (CO and CH)4) For Ca2Fe2O5The influence of the reduction stage of the oxygen carrier;
FIG. 8 shows chemical looping combustion 10 CO reductions with O2An oxidation cycle experiment;
FIG. 9 is chemical looping combustion 10 CH4Reduction with O2An oxidation cycle experiment;
FIG. 10 shows the chemical looping hydrogen production for 20 CO reductions with H2O oxidation cycle experiment;
FIG. 11 shows the hydrogen concentration in 10 cycles in the chemical looping hydrogen production process;
FIG. 12 shows the oxygen carrier conversion for 20 cycles in a chemical looping hydrogen production process;
FIG. 13 shows 20 chemical looping hydrogen production reduction stages Ca2Fe2O5Oxygen carrierThe body conversion rate;
FIG. 14 shows CaO + Fe carrier conversion for 20 chemical looping hydrogen oxidation stages;
FIG. 15 shows the results of XRD experiments of ferrites at different reduction stages and cycle times;
FIG. 16 shows a composite calcium-iron oxygen carrier Ca2Fe2O5Two-step method chemical chain hydrogen production cooperated with CO2Schematic gas capture.
Detailed Description
The invention is further described with reference to the following examples and the accompanying drawings.
Example 1:
the method comprises the following steps:
1) using Ca2Fe2O5CO is used as a reducing agent as an oxygen carrier, and the oxygen carrier is reduced to the state of Fe and CaO and simultaneously the CO is captured in a fuel reactor at 850 DEG C2A gas;
2) the reduced Fe and CaO pass through a steam reactor, and are oxidized by water vapor to generate Ca in one step with a fuel reactor at 900 DEG C2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 2
1) Using Ca2Fe2O5As oxygen carrier, CH4As a reducing agent, an oxygen carrier is reduced to Fe and CaO states at 880 ℃ in a fuel reactor, and CO is captured at the same time2；
2) The reduced Fe and CaO pass through a steam reactor, are oxidized by steam at the temperature of 920 ℃, and then Ca is generated in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 3
1) Using Ca2Fe2O5As oxygen carriers, H2CO and CH4Synthesis gas as reducing agent, reacting with fuel at 950 deg.CReducing the oxygen carrier into Fe and CaO states and simultaneously trapping CO2；
2) The reduced Fe and CaO pass through a steam reactor, are oxidized by water vapor at 950 ℃, and then Ca is generated in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 4
1) Using Ca2Fe2O5As oxygen carriers, CO and CH4The synthetic gas is used as a reducing agent, and is reacted with fuel in a reactor at 880 ℃ to reduce an oxygen carrier into Fe and CaO states and capture CO2；
2) The reduced Fe and CaO pass through a steam reactor, are oxidized by water vapor at the temperature of 900 ℃, and then Ca is generated in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 5
1) Using Ca2Fe2O5As oxygen carriers, CO and H2The synthesis gas is used as a reducing agent, and is reacted with fuel in a reactor at 920 ℃ to reduce an oxygen carrier into Fe and CaO states and capture CO2；
2) The reduced Fe and CaO pass through a steam reactor, are oxidized by steam at the temperature of 920 ℃, and then Ca is generated in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 6
1) Using Ca2Fe2O5As oxygen carrier, CH4And H2As a reducing agent, an oxygen carrier is reduced to Fe and CaO states at 890 ℃ in a fuel reactor, and CO is captured at the same time2；
2) The reduced Fe and CaO pass through a steam reactor, are oxidized by water vapor at 950 ℃, and then Ca is generated in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 7
1) Using Ca2Fe2O5As an oxygen carrier, gas after coal gasification is used as a reducing agent, the oxygen carrier is reduced to Fe and CaO states at 875 ℃ in a fuel reactor, and CO is captured at the same time2；
2) The reduced Fe and CaO are oxidized by water vapor at 850 ℃ in a steam reactor to generate Ca in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 8
1) Using Ca2Fe2O5As an oxygen carrier, gas generated after coal pyrolysis is used as a reducing agent, the oxygen carrier is reduced to Fe and CaO states at 875 ℃ in a fuel reactor, and CO is captured at the same time2；
2) The reduced Fe and CaO are oxidized by water vapor at 850 ℃ in a steam reactor to generate Ca in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 9
1) Using Ca2Fe2O5As an oxygen carrier, gas after biomass gasification is used as a reducing agent, the oxygen carrier is reduced to Fe and CaO states at 875 ℃ in a fuel reactor, and CO is captured at the same time2；
2) The reduced Fe and CaO are oxidized by water vapor at 925 ℃ in a steam reactor to generate Ca in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
Example 10
1) Using Ca2Fe2O5AsReducing the oxygen carrier into Fe and CaO states at 875 ℃ in a fuel reactor by using gas obtained after biomass pyrolysis as a reducing agent and simultaneously trapping CO2；
2) The reduced Fe and CaO are oxidized by water vapor at 925 ℃ in a steam reactor to generate Ca in one step2Fe2O5While generating high concentration hydrogen. The above steps are repeated, so that two-step chemical chain hydrogen production circulation is realized to cooperate with CO2And (4) trapping.
The invention proposes to use Ca2Fe2O5As an oxygen carrier for chemical looping hydrogen production, the oxygen carrier is used for the chemical looping hydrogen production in cooperation with CO2And (4) trapping. FIG. 1 shows Ca2Fe2O5H of oxygen carrier2TPR graph, from which Ca is known from the results of TPR experiments2Fe2O5Tends to be reduced to Fe and CaO in one step. While using Fe2O3When used as an oxygen carrier, it is necessary to pass through Fe2O3→Fe3O4After the multi-step reduction of → FeO → Fe, Fe for hydrogen production can be obtained. FIG. 2 is Fe2O3With Ca2Fe2O5The reduction performance was compared with each other, and it was found that iron oxide and Ca were present in the first half of the reduction stage2Fe2O5Has almost the same reaction performance, and Ca increases with time2Fe2O5The reaction performance of the catalyst is obviously higher than that of Fe2O3In the same time, the reduction degree is obviously improved. According to the above analysis, taking CO as an example of the reducing agent, two chemical reaction equations are shown for the reduction process of different oxygen carriers:
Fe2O3reduced by CO as oxygen carrier:
Ca2Fe2O5reduced by CO as oxygen carrier:
FIG. 3 shows XRD results at different reduction times in the consent phase, and it can be seen that at 5 minutes, 10 minutes, and 20 minutes of reduction time, mainly unreacted Ca is present in the material2Fe2O5And CaO and Fe generated after reduction with CO. The results further demonstrate that Ca2Fe2O5During the reduction process of the oxygen carrier, the intermediate valence state is not changed, and the oxygen carrier can be directly reduced into CaO and Fe. In addition, the reduction performance of the oxygen carrier under different influence factors is researched, and the results are shown in FIGS. 4-7, which represent the reduction performance of methane and Ca under different CO concentrations, different reduction temperatures and different oxygen carriers2Fe2O5Under oxygen carriers, the influence of different reducing agents on the reducing properties thereof. Through investigation on the influence of different factors, the optimum operating conditions and working conditions are found out, the reduction rate is ensured, and simultaneously, a large amount of carbon deposition in the reduction process is avoided.
Ca2Fe2O5The catalyst is used as an oxygen carrier for chemical-looping hydrogen production or chemical-looping combustion, and has better oxygen carrying capacity. As shown in FIGS. 8 and 9, the reduction with CO + O2Oxidation with CH4Reduction + O2Ten chemical looping combustion experiments of oxidation. It can be seen that Ca is used2Fe2O5As oxygen carriers, both CO and CH4As reducing agents, the carbon deposits are less and the circulation stability is stronger in the reduction stage adopting CO as the reducing agent according to thermogravimetric experimental data. And adopt CH4As a reducing stage of the reducing agent, Ca2Fe2O5When reduced completely or nearly completely, the mass of the product increasesThe length is more serious, and the mass gradually tends to be stable after increasing to a certain degree. This partial mass growth is due to the formation of iron carbide. Using Fe2O3When the iron carbide is used as an oxygen carrier, the reaction equation of the generated iron carbide is as follows:
the iron carbide formed is oxidized with H2O reacts to form Fe3O4：
Ca2Fe2O5When CO is used as an oxygen carrier and CO is used as a reducing agent, the mass of the oxygen carrier is increased after long-time reduction of CO, and Fe is not detected in an XRD result3The presence of C, and therefore the increase in mass of this fraction, is due to the disproportionation of CO gas to produce CO2Gas and C, and further carbon deposition on the oxygen carrier. The oxygen carrier is in a staged state at the rear part of the reduction, the oxygen carrier is almost completely reduced, the oxidation is lost, and the disproportionation reaction of CO is caused. However, the amount of the carbon deposition is small, and the carbon deposition can be effectively controlled or avoided by determining the reactivity of the oxygen carrier and adjusting the concentration and the reaction time of the corresponding reducing agent. And adopt CH4As a reducing agent, XRD experimental results confirmed the formation of iron carbide. The iron carbide formed is oxidized with steam or O2The reaction is carried out to generate Fe ions with unsaturated valence, and the Fe ions can be continuously oxidized in the presence of CaO to finally generate Ca2Fe2O5I.e. the ferric state.
As shown in fig. 10, it is a graph of the results of 20 two-step chemical looping hydrogen production experiments using CO gas as a reducing agent and water vapor as an oxidizing agent under thermogravimetric conditions. The figure fully proves that the chemical chain hydrogen production of the composite calcium-iron oxygen carrier is cooperated with CO2A trapping method. After 20 times of circulating CO reduction and H2After the oxidation reaction of O, the oxygen carrier still remains quiteGood stability. As shown in fig. 11, the results of 10 chemical looping hydrogen production experiments using a fixed bed as a chemical looping hydrogen production reactor and a novel calcium-iron catalyst as an oxygen carrier. The average concentration of hydrogen was maintained above 99%. The catalyst is prepared by a citric acid high-temperature foaming method, and the catalyst has certain carbon deposition and calcium carbonate, so that in the first hydrogen production stage, the carbon deposition can react with water vapor to generate a certain amount of CO gas to influence the concentration of hydrogen:
fig. 12-14 are graphs showing statistics of oxygen carrier conversion rate for 20 times, oxygen carrier conversion rate for different times in the reduction stage, and oxygen carrier conversion rate for the oxidation stage, respectively, under a chemical looping hydrogen production reactor using thermogravimetry. According to the experimental result, the oxygen carrier has stable conversion rate and strong reactivity in 20 oxidation-reduction stages, and is a prospect oxygen carrier of the two-step chemical-looping hydrogen production technology.
Conventional chemical looping hydrogen production techniques, from Fe2O3Or modified Fe2O3As oxygen carrier, the oxygen carrier is reduced into Fe or FeO through a fuel reactor, and the oxygen carrier is oxidized into Fe through a steam reactor3O4And the air reactor is further oxidized to Fe2O3Realizes the three-step reduction and oxidation of the iron-based oxygen carrier and the chemical-looping hydrogen production under the iron-based oxygen carrier to cooperate with CO2And (4) trapping. The composite calcium-iron oxygen carrier and the chemical chain hydrogen production thereof cooperate with CO2Trapping method, proposed to use Ca2Fe2O5As a chemical chain hydrogen production oxygen carrier, and conventional Fe2O3Fe as compared with its modified oxygen carrier0Can be oxidized into Fe in one step3+Therefore, an air reactor in the traditional chemical looping hydrogen production can be omitted. The oxygen carrier can realize the chemical looping hydrogen production and the CO coordination only by two steps of reduction of the fuel reactor and oxidation of the steam reactor2And the hydrogen production can be improved by 12.5 percent under the condition that the hydrogen production amount is the same as the mole number of the iron and is completely reduced in the reduction stage. And due to the omission of air reactionThe cost of the chemical-looping hydrogen production process is greatly reduced, the abrasion degree of the oxygen carrier in the reactor is also greatly reduced with the same cycle number, and the energy loss of the whole reaction cycle can be reduced by reducing the reactor. The net reaction equations for the two chemical looping hydrogen production methods are as follows:
traditional three-step chemical looping hydrogen production:
CO+8/9H2O+1/18O2→CO2+8/9H2(formula 8)
Novel two-step chemical chain hydrogen production:
CO+H2O→CO2+H2(formula 9)
Therefore, in the traditional chemical looping hydrogen production method, a part of fuel is used for combustion to provide system heat, and in the novel chemical looping hydrogen production method provided by the invention, the fuel directly reacts with water to produce hydrogen, the products are all target products, and CO generated in a fuel reactor is used as CO2While being trapped, the steam reactor produces high concentration H2。
The above examples are only preferred embodiments of the present invention, it should be noted that: it will be apparent to those skilled in the art that various modifications and equivalents can be made without departing from the spirit of the invention, and it is intended that all such modifications and equivalents fall within the scope of the invention as defined in the claims.
Claims (2)
1. Composite calcium-iron oxygen carrier and chemical-looping hydrogen production synergistic CO thereof2A trapping method, characterized by comprising the steps of:
1) using Ca2Fe2O5As an oxygen carrier, the oxygen carrier and a reducing agent are subjected to oxygen carrier reduction reaction in a fuel reactor at the temperature of 850-950 ℃, Fe and CaO states are obtained by reduction, and CO generated by the oxygen carrier reduction reaction is captured at the same time2The reducing agent is: CO, H2、CH4And CO2A mixture of two or more of;
2) feeding the reduced Fe and CaO into a steam reactor as an oxygen carrier, reacting at 850-950 deg.CCarrying out oxygen carrier oxidation reaction on water vapor serving as an oxidant to obtain Ca2Fe2O5Simultaneously trapping high-concentration hydrogen generated by the oxidation reaction of the oxygen carrier and obtaining Ca2Fe2O5And returned to the fuel reactor.
2. The composite calcium-iron oxygen carrier and the chemical chain hydrogen production synergistic CO thereof according to claim 12The capture method is characterized in that the fuel reactor and the steam reactor both adopt fluidized bed reactors.
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