Biogas residue pyrolysis chemical chain reforming in-situ clean power generation method and device

Abstract

The invention discloses a biogas residue pyrolysis chemical chain reforming in-situ clean power generation method and device. The system comprises a pretreatment unit, a pyrolysis gasification unit, a chemical chain reforming power generation device, a combustor and a tail gas collection device. The biogas residues are subjected to solid-liquid separation, the moisture content is reduced to 20%-30%, the biogas residues are air-dried to be lower than 10% for pyrolysis gasification, generated pyrolysis gas enters a partitioned reaction hearth, the upper portion is a pyrolysis gas area, and the lower portion is an oxygen carrier anode. An anode is supported by a Ni / nYSZ composite matrix, a Bi2O3 ceramic electrolyte layer and a FeCo2O4-based cathode are integrated, and an oxygen carrier is a composite perovskite catalyst LaxA < 1-x > FeyB < 1-y > O3. After external electric heating is started, a combustor recycles tail gas heat to maintain reaction, tail gas is separated to obtain H2O for cyclic utilization and CO2 resourceful treatment, and an external circuit system achieves power generation and monitoring. The device synchronously completes power generation and gas conversion through chemical chain reforming, has high-temperature-resistant stability and a multi-stage resource recovery function, remarkably improves biogas residue energy conversion efficiency and reduces carbon emission.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical chaining hydrogen production, clean fuel conversion and functional materials, and in particular to a method and device for in-situ clean power generation by pyrolysis and chemical chaining reforming of biogas residue. Background Art

[0002] The global energy system is undergoing profound changes, and energy security, environmental pollution and climate change have become issues of common concern to the world. At present, China is the world's largest energy producer and consumer. The long-term coal-based energy structure has led to a high total carbon emission. Faced with the severe challenges of climate change and the implementation of the "dual carbon" goals (carbon peak and carbon neutrality), China must accelerate the process of promoting clean and low-carbon energy. If traditional coal-fired power plants adopt conventional carbon capture technology, the power generation efficiency will drop significantly by 10%-15%, which further promotes the demand for new clean and efficient carbon-based fuel power generation technologies. Advanced energy conversion technologies such as chemical chain combustion and solid oxide fuel cells have shown great application prospects in achieving energy transformation and carbon neutrality goals due to their high efficiency and low carbon characteristics, and provide important technical support for global energy sustainable development.

[0003] Biogas residue is a semi-solid by-product produced during anaerobic digestion, mainly composed of undecomposed organic matter, microbial residues and minerals. With the rapid development of the biogas industry, the output of biogas residue has increased year by year. However, biogas residue that has not been effectively treated may contain pathogenic microorganisms and harmful substances. If it enters the environment directly, it will not only cause pollution, but also hinder the further promotion of biogas projects. Therefore, how to reasonably and efficiently utilize and treat biogas residue has become an important issue that needs to be solved urgently. At present, traditional disposal methods are mainly based on returning agricultural fertilizers to the fields, but the added value is low. In order to improve the utilization value of biogas residue, researchers have developed a series of high-value utilization technologies. Chinese invention patent CN111592420A discloses a method for preparing composite carbon-based fertilizers using biogas slurry and biogas residue. The biogas residue is prepared into a composite carbon material through slaked lime pretreatment and high-temperature carbonization, and is used to enrich the nutrients in the biogas slurry to make high-efficiency carbon-based fertilizers. The product shows significant advantages in improving soil structure and increasing crop yields. Chinese patent CN111690691A proposes a two-stage process for the resource utilization of biogas residue and biogas liquid wastewater. Through ammoniation pretreatment and dry anaerobic fermentation technology, the biogas residue is converted into high-efficiency energy, and the resource recovery of ammonia nitrogen in the biogas liquid is achieved, which significantly improves the treatment efficiency and economic benefits. In addition, patent CN202010310563.5 uses biogas residue to carry out pyrolysis in the presence of a catalyst, which significantly improves the synthesis gas yield and pyrolysis efficiency, providing a new idea for clean energy production. Overall, biogas residue resources have huge development potential. The diversified and high-value utilization direction from agriculture to energy not only promotes the resource and energy process of waste, but also provides important support for the realization of clean production and sustainable development. Against the backdrop of the carbon neutrality goal, the high-value utilization of biogas residue will surely inject new vitality into the development of the green economy and show broad application prospects.

[0004] Solid oxide fuel cell (SOFC) is a highly efficient power conversion device that can directly convert the chemical energy of hydrogen or hydrocarbon fuel into electrical energy, with a power generation efficiency of up to 50%-60%. If waste heat is used in conjunction with a gas turbine, the overall power generation efficiency can be further increased to 60%-70%, far exceeding the level of 30%-40% of traditional thermal power generation, and has broad application prospects. However, the hydrogen required for SOFC currently mainly relies on fossil fuel steam reforming or water electrolysis to produce hydrogen. These technologies have high energy consumption, large carbon emissions and high costs, which restrict the economy and large-scale application of SOFC. In contrast, biogas residue chemical chaining reforming technology efficiently transfers oxygen through solid oxygen carriers to achieve fuel conversion and hydrogen preparation, while directly separating carbon dioxide, which can significantly reduce energy consumption and carbon emissions. Coupling chemical chaining reforming with SOFC can not only provide low-cost hydrogen, but also improve the overall efficiency of the system, promoting the sustainable development and large-scale application of SOFC.

[0005] In the prior art, the coupling modes of chemical chaining combustion and fuel cells mainly include the direct connection of chemical chaining combustion and power generation systems and the combination of chemical chaining gasification and fuel cells, but there are significant technical deficiencies. On the one hand, in the process of combining traditional chemical chaining combustion with power generation systems, the reaction temperature is high and the heat recovery efficiency is low, making it difficult to achieve efficient energy conversion; the carbon dioxide separation and purification process is complicated, further increasing the operating cost. In response to the above problems, the present invention proposes an in-situ clean power generation method and device based on chemical chaining reforming of biogas residue pyrolysis. By innovatively integrating chemical chaining reforming with SOFC, direct in-situ power generation of carbon-containing pyrolysis gas is directly achieved, and the tail gas waste heat recovery module and intelligent control system are integrated, which not only overcomes the limitations of traditional technologies, but also significantly improves the resource and energy utilization efficiency of biogas residue. Summary of the invention

[0006] The present invention proposes a method and device for in-situ clean power generation by pyrolysis and chemical chain reforming of biogas residues, which integrates chemical chain reforming with SOFC, directly realizes in-situ power generation of carbon-containing pyrolysis gas, and prepares pyrolysis gas by pyrolysis and gasification of biogas residues, providing efficient and clean fuel for fuel cells. The anode (oxygen carrier) provides lattice oxygen for chemical chain reforming, and releases electrons to the cathode through an external circuit to form current. This method solves the problems of low thermal efficiency, impurity pollution and complex carbon separation of traditional coupling methods, and provides an efficient path for clean energy conversion.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] In the first aspect, the present invention provides a method and device for in-situ clean power generation by pyrolysis and chemical looping reforming of biogas residues, including biogas residue pretreatment, pyrolysis and gasification, a burner, a chemical looping reforming in-situ clean power generation device, an external electric heating system, an external circuit power consumption / detection system, and a collection device.

[0009] The biogas residue pretreatment method is characterized in that: the biogas residue is first subjected to solid-liquid separation treatment to remove excess water and separate the biogas liquid. The water content of the biogas residue is reduced to about 20%-30% by mechanical filter pressing or centrifugal separation. After solid-liquid separation, the water content of the biogas residue can be further reduced by air drying or sun drying. The water content is reduced to below 10% by natural air drying or mechanical dehydration, providing suitable raw materials for the subsequent pyrolysis process.

[0010] The chemical loop reforming in-situ clean power generation device comprises a chemical loop reforming reaction furnace, an anode (oxygen carrier), an anode support part, a solid oxide electrolyte layer and a cathode.

[0011] The external circuit power consumption / detection system includes an external circuit system and electrical appliances or related detection systems connected to the cathode and anode of the chemical chain reforming in-situ clean power generation device; the external electric heating system is used to heat the chemical chain reforming in-situ clean power generation device to reach the temperature required for the reaction.

[0012] The burner and the collecting device are characterized in that: the burner burns the tail gas generated in the reaction process to provide heat for the chemical chain reforming in-situ clean power generation device, and a burner is set to recover heat as needed to provide the required heat for the subsequent chemical chain reforming; the collecting device collects the H generated in the reaction process of the chemical chain reforming in-situ clean power generation device 2 O and CO 2 Collect, collect H 2 O can be recycled for system cooling to improve water resource utilization; CO 2 It can be used to produce chemical raw materials (such as carbonates), further realizing resource utilization.

[0013] In some embodiments, chemical chain reforming uses oxygen carrier materials based on perovskite oxides to improve the stability of the reaction and the oxygen transfer efficiency, and can achieve efficient hydrogen production at a lower temperature. The oxygen carrier used is a composite perovskite catalyst with the chemical formula of La x A 1-x Fe y B 1-y O 3 , wherein the A position is selected from one of Na and Li; the B position is selected from one of Ni, Mn, and Co; 0<x<1, 0<y<1.

[0014] Furthermore, the present invention adopts a citric acid sol-gel method to prepare a composite perovskite-type oxygen carrier La x A 1-x Fe y B 1- y O 3 3. The specific preparation method is: firstly, analyze the pure La(NO 3 ) 3 6H 2 O, A source metal salt, Fe(NO 3 ) 3 9H 2O and B source metal salts are dissolved in deionized water according to a stoichiometric ratio and stirred thoroughly to mix evenly. Then, an appropriate amount of citric acid is added as a complexing agent, and stirring is continued until the solution is transparent to form a uniform precursor solution. Next, the precursor solution is dried at 80°C until the solvent is completely evaporated to obtain a viscous gel. Finally, the gel is calcined at 600°C for 4 hours, ground and screened after cooling to obtain the desired composite perovskite catalyst. By selecting a specific alkali metal element at the A position, the structural stability of the perovskite oxide can be moderately reduced, and the catalytic activity and electron transfer ability of the oxygen carrier can be improved; when elements such as Cu, Mn or Zn are selected at the B position, the stability of the perovskite metal oxide is further destroyed, more active sites are exposed, the catalytic performance is effectively improved, and the product distribution is improved. The composite perovskite catalyst exhibits excellent catalytic performance in the chemical chain reforming process, and can efficiently and cleanly convert the chemical energy of biogas residue into electrical energy.

[0015] Furthermore, the anode support of the chemical chain reforming in-situ clean power generation device adopts a Ni / nYSZ composite anode matrix, the Ni phase provides electronic conductivity, the YSZ phase provides ionic conductivity, and its three-dimensional network structure serves as the entire anode structure support unit; the electrolyte layer adopts a bismuth oxide-based (Bi 2 O 3 ) ceramics are fluorite-type electrolytes; the cathode uses FeCo 2 O 4- x Ce 0.8 Sm 0.2 O 1.9 (x=0, 30, 40, 50, 60, 70 wt.%) composite oxides.

[0016] Furthermore, the thickness of the anode support is 300 to 900 μm, and the mass composition range is 85 / 35 to 65 / 55. The specific preparation method is as follows: First, select an analytically pure nickel source (such as NiO) and yttrium-doped stabilized zirconia (nYSZ) powder and mix them according to a molar ratio. Add an appropriate amount of deionized water to the mixed powder and perform ball milling to ensure uniform dispersion of the two materials. Then, the ball-milled mixture is dried to obtain a dry powder. Next, the dry powder is coated on a suitable substrate by tape casting to form a thin film to ensure uniformity and thickness control of the anode. Finally, the coated anode film is sintered at a temperature of 1200°C for 4 hours to form a composite anode support with a three-dimensional network structure, which not only ensures the mechanical strength of the anode, but also provides good electronic conductivity and ionic conductivity.

[0017] Furthermore, the electrolyte layer is based on bismuth oxide (Bi 2 O 3) ceramics, having a fluorite structure. The preparation method is as follows: first, select a high-purity bismuth source (such as Bi 2 O 3 ) and dissolved in a suitable solvent, adding an appropriate amount of citric acid as a complexing agent, and stirring to react the bismuth source with the citric acid to form a uniform sol. Then, the sol is dried at 80°C to obtain a gel precursor. The gel is sintered at 600°C for 4 hours to form a bismuth oxide-based ceramic electrolyte with good oxygen ion conductivity.

[0018] Furthermore, the cathode is made of FeCo 2 O 4-x Ce 0.8 Sm 0.2 O 1.9 (x = 0, 30, 40, 50, 60, 70 wt.%) composite oxide. The preparation method is as follows: first, select a high-purity iron source (such as Fe(NO 3 ) 3 9H 2 O), cobalt sources (such as Co(NO 3 ) 2 6H 2 O), cerium source (such as Ce(NO 3 ) 3 6H 2 O) and samarium sources such as Sm(NO 3 ) 3 6H 2 O), dissolving these metal salts in deionized water. Then, using ammonia water to adjust the pH value of the solution, the metal ions undergo a coprecipitation reaction to obtain a precipitate. The precipitate is filtered, washed to neutrality, dried at low temperature, and sintered at 1000°C for 4 hours to obtain the desired FeCo 2 O 4- x Ce 0.8 Sm 0.2 O 1.9 Composite oxide cathode material. This material has excellent catalytic properties, can effectively promote oxygen reduction reactions, and improve the electrochemical performance of batteries.

[0019] The anode, electrolyte layer and cathode materials prepared by the above method can effectively improve the overall performance of the chemical chain reforming in-situ clean power generation device and ensure its stability and efficient operation under high temperature conditions.

[0020] Furthermore, the reaction temperature of the chemical loop reforming in-situ clean power generation device is 800-950° C. In one reaction cycle, the chemical loop reforming reaction time is 30-70 minutes, and the fuel cell reaction power supply time is 20-60 minutes.

[0021] The beneficial effects achieved by one or more embodiments of the present invention are as follows:

[0022] The chemical chain reforming in-situ clean power generation device of the present invention is not limited by the source and type of fuel. As a low-cost and renewable biomass resource, biogas residue can be directly used for pyrolysis and reforming to generate H 2 The synthesis gas mainly composed of CO is used for subsequent fuel cell power generation.

[0023] The present invention solves the problems of low thermal efficiency, serious impurity pollution and complex operation control existing in the coupling of traditional chemical chain and fuel cell through the innovative coupling design of biogas slag chemical chain technology and fuel cell, and provides an efficient, safe and sustainable technical path for the development and utilization of clean energy. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of the process of the present invention.

[0025] Figure 2 The structure diagram of the chemical loop reforming in-situ clean power generation device. The following are marked in the figure: 1. heating source; 2. furnace; 3. anode (oxygen carrier); 4. anode support; 5. solid oxide electrolyte; 6. cathode. DETAILED DESCRIPTION

[0027] The following is combined with Figure 1 and attached Figure 2 The preferred embodiments of the present invention are described in detail to make the advantages and features of the present invention easier to be understood by those skilled in the art, thereby making a clearer and more definite definition of the protection scope of the present invention. Example 1

[0028] The oxygen carrier material is a perovskite-type composite oxide, whose chemical formula is La 0.8 Na 0.2 Fe 0.6 Mn 0.4 O 3 , where Na is selected at position A and Mn is selected at position B. The preparation method is as follows: first, select analytically pure La(NO 3 ) 3 6H 2 O, A-site metal salt NaNO 3 、Fe(NO 3 ) 3 9H 2 O and B-site metal salts Mn(NO 3 ) 2 ·4H 2O is dissolved in deionized water according to a stoichiometric ratio and stirred to form a uniform solution; subsequently, an appropriate amount of citric acid is added to the solution as a complexing agent, the molar ratio of citric acid to metal ions is controlled to be 1:1 to 1.5:1, and stirring is continued until the solution is clear and transparent; the prepared precursor solution is placed in an 80°C water bath for heating and drying, and a viscous gel is formed after the solvent is completely evaporated; the obtained gel is placed in a 600°C high-temperature furnace for calcination for 4 hours, and after cooling, it is ground and screened to prepare a composite perovskite-type oxygen carrier powder with uniform crystal form and suitable particle size.

[0029] preparation Figure 2 The chemical chain reforming in-situ clean power generation device shown in the figure. The anode support material is Ni / nYSZ composite, and the specific preparation method is: select analytically pure NiO and yttrium-doped stabilized zirconia (Y 2 O 3 -ZrO 2 , YSZ) powder, mixed according to the molar mass ratio of 85 / 35 to 65 / 55, added with appropriate amount of deionized water for ball milling, the ball milling time is 4 to 6 hours to ensure uniform distribution of the material; the ball-milled slurry is prepared into powder by spray drying, and then the dry powder is evenly coated on the surface of the substrate by tape casting, and the coating thickness is controlled to be 300 to 900μm; finally, the coated anode film is placed in a high-temperature furnace at 1200℃ and sintered for 4 hours to prepare a composite anode matrix with a three-dimensional network structure, ensuring that it has excellent mechanical strength and conductive properties. The electrolyte layer uses bismuth oxide-based ceramic material, and its preparation method is as follows: analytical pure Bi 2 O 3 Dissolve in an appropriate amount of deionized water, add citric acid as a complexing agent, the molar ratio of citric acid to bismuth ion is 1:1, stir evenly to form a sol; dry the obtained sol at 80°C to form a gel, and calcine the gel at 600°C for 4 hours to obtain a fluorite-type structured bismuth oxide-based ceramic electrolyte powder. The cathode material is FeCo 2 O 4-x Ce 0.8 Sm 0.2 O 1.9 The composite oxide is prepared by: 3 ) 3 9H 2 O、Co(NO 3 ) 2 6H 2 O、Ce(NO 3 ) 3 6H 2 O and Sm(NO 3 ) 3 6H 2O was dissolved in deionized water according to a stoichiometric ratio, and the pH value of the solution was adjusted to 7-9 to allow the metal ions to undergo a coprecipitation reaction to obtain a precipitate; the precipitate was filtered, washed to neutrality, and then dried, and then sintered in a high-temperature furnace at 1000°C for 4 hours to prepare FeCo 2 O 4-x Ce 0.8 Sm 0.2 O 1.9 Composite oxide powder, the material has good oxygen reduction catalytic performance and high temperature stability. The oxygen carrier, anode, electrolyte layer and cathode material prepared by the above preparation method can effectively improve the electrochemical performance and operation stability of the chemical chain reforming in-situ clean power generation device.

[0030] At the beginning of the reaction, the synthesized oxygen carrier is first placed in the furnace, and the heating source reaction temperature is set to 800℃, and the heating rate is 20℃ / min. After the temperature reaches the set value, the pyrolysis gas is turned on to allow the pyrolysis gas to react with the oxygen carrier in the furnace for a chemical chain reforming reaction. The reaction time is 40 minutes. After the lattice oxygen in the oxygen carrier reacts, the tail gas is discharged from the outlet. When the external circuit is turned on, the oxygen in the air obtains electrons at the cathode to form O 2- , and then the electrolyte conducts to the anode, where the oxygen carrier after the reaction is reoxidized on the anode surface, restoring the lattice oxygen of the oxygen carrier and releasing electrons to the external circuit. The electrons reach the cathode through the circuit, and the electrochemical reaction continues. After the oxygen carrier reaction is completed, the above chemical chain reforming process is repeated, and the two reactions are carried out alternately to achieve chemical chain reforming in-situ clean power generation. Table 1 Implementation conditions and results of chemical looping reforming in-situ clean power generation process Example 2

[0031] The oxygen carrier material is a perovskite-type composite oxide, whose chemical formula is La 0.8 Na 0.2 Fe 0.6 Mn 0.4 O 3 , where Li is selected at position A and Co is selected at position B. The preparation method is as follows: first, select analytically pure La(NO 3 ) 3 6H 2 O, A-site metal salt LiNO 3 、Fe(NO 3 ) 3 9H 2 O and B-site metal salts Co(NO 3 ) 2 ·4H 2O is dissolved in deionized water according to a stoichiometric ratio and stirred to form a uniform solution; subsequently, an appropriate amount of citric acid is added to the solution as a complexing agent, the molar ratio of citric acid to metal ions is controlled to be 1:1 to 1.5:1, and stirring is continued until the solution is clear and transparent; the prepared precursor solution is placed in an 80°C water bath for heating and drying, and a viscous gel is formed after the solvent is completely evaporated; the obtained gel is placed in a 600°C high-temperature furnace for calcination for 4 hours, and after cooling, it is ground and screened to prepare a composite perovskite-type oxygen carrier powder with uniform crystal form and suitable particle size.

[0032] Since the anode support material, electrolyte layer, cathode material and reaction conditions are the same as those in Example 1, they are not described again here. Embodiments 3 to 6

[0033] The differences between the preparation conditions of Examples 3 to 6 and Example 1 are shown in Table 1 below:

[0034] The difference between Example 3 and Example 1 is that the reaction temperature is 800° C. and the chemical loop reforming reaction time is 50 min.

[0035] The difference between Example 4 and Example 1 is that the reaction temperature is 900° C., the chemical chain reforming reaction time is 50 minutes, and the clean power generation time is 60 minutes.

[0036] The difference between Example 5 and Example 1 is that different proportions of metal combinations are used in the preparation process of the oxygen carrier.

[0037] The difference between Example 6 and Example 1 is that different proportions of metal combinations are used in the preparation process of the oxygen carrier.

[0038] The above embodiments are only examples provided to illustrate the present invention and are not intended to limit the specific implementation methods. For those of ordinary skill in the art, other forms of changes or variations may be made based on the above description. These obvious changes or variations, without the need to list them one by one, all belong to the protection scope of the present invention.

Claims

1. A method and device for in-situ clean power generation by pyrolysis and chemical chain reforming of biogas residue, characterized in that: It includes sludge pretreatment, pyrolysis and gasification, burner, chemical chain reforming in-situ clean power generation device, external electric heating system and external circuit power / detection system, and collection device.

2. The biogas residue pretreatment method according to claim 1, characterized in that: The biogas residue is first subjected to solid-liquid separation to remove excess water and separate the biogas liquid. The moisture content of the biogas residue is reduced to about 20%-30% by mechanical filter pressing or centrifugal separation. After solid-liquid separation, the moisture content of the biogas residue can be further reduced by air drying or sun drying. The moisture content is reduced to below 10% by natural air drying or mechanical dehydration, providing suitable raw materials for the subsequent pyrolysis process.

3. The chemical loop reforming in-situ clean power generation device according to claim 1 is characterized by: The chemical looping reforming in-situ clean power generation system comprises a chemical looping reforming reaction furnace, an anode (oxygen carrier), an anode support part, a solid oxide electrolyte layer and a cathode.

4. The external electric heating system and the external circuit power / detection system according to claim 1, characterized in that: The external circuit power consumption / detection system includes an external circuit system and electrical appliances or related detection systems connected to the cathode and anode of the chemical chain reforming in-situ clean power generation device; the external electric heating system is used to heat the chemical chain reforming in-situ clean power generation device to reach the temperature required for the reaction.

5. The burner and collector device according to claim 1, characterized in that: The burner burns the tail gas generated during the reaction to provide heat for the chemical chain reforming in-situ clean power generation device. The burner is set to recover heat as needed to provide the required heat for subsequent chemical chain reforming. The collection device collects H2O and CO2 generated during the reaction of the chemical chain reforming in-situ clean power generation device. The collected H2O can be recycled for system cooling to improve the utilization rate of water resources; CO2 can be used to produce chemical raw materials (such as carbonates) to further realize resource utilization.

6. According to claim 3, the chemical chain reforming reaction furnace comprises an oxygen carrier material inlet (including a pyrolysis gas inlet) and an exhaust gas outlet; the reforming reaction furnace is a cylindrical structure, made of high-temperature resistant metal materials, and is divided into two parts, the upper part is the pyrolysis gas zone, and the lower part is the anode and also the oxygen carrier, and the lower part is connected to the anode support by a high-temperature resistant aluminum-silver conductive adhesive.

7. The anode support of the chemical loop reforming in-situ clean power generation device according to claim 3 adopts a Ni / nYSZ composite anode substrate, wherein the Ni phase provides electronic conductivity, the YSZ phase provides ionic conductivity, and its three-dimensional network structure serves as the entire anode structure support unit; the bismuth oxide-based (Bi2O3) ceramic used in the electrolyte layer is a fluorite-type electrolyte; the cathode adopts FeCo2O 4-x Ce 0.8 Sm 0.2 O 1.9 (x=0, 30, 40, 50, 60, 70 wt.%) composite oxides.

8. The method and device for in-situ clean power generation by pyrolysis and chemical looping reforming of biogas residue according to claim 1, characterized in that: The anode (oxygen carrier) used is a composite perovskite catalyst with the chemical formula of La x A 1-x Fe y B 1-y O3, wherein the A position is selected from one of Na and Li; the B position is selected from one of Ni, Mn and Co; 0<x<1, 0<y<1.

9. The method for preparing the composite perovskite anode (oxygen carrier) according to claim 8, characterized in that: Analytically pure nitrates of La, A, Fe and B are dissolved in deionized water according to their stoichiometric ratio, fully stirred and mixed, and a reaction complexing agent is added to obtain a precursor solution of a composite perovskite anode (oxygen carrier); the composite perovskite anode (oxygen carrier) precursor is stirred until viscous and then dried at 80°C to obtain a gel; the gel is calcined at 700°C, ground after cooling, and screened and separated to obtain the composite perovskite anode (oxygen carrier). The nickel-based, manganese-based, and iron-based oxygen carriers are oxygen carriers suitable for conventional chemical chain reforming reactions.

Images