Combined system and method for CO2 reduction to produce carbon black and cyclic power generation

Abstract

The present invention provides a combined system for producing carbon black by reducing CO2 and generating power by circulation and an operation method. The system comprises: a SOFC module, a carbon layer is gasified by water vapor and CO2 to produce fuel gas H2 and CO, and O2 is introduced into the first air electrode of the SOFC module, and O2 is ionized to produce O 2‑ The fuel gas is mixed with O at the first fuel electrode of the SOFC module. 2‑ The reaction generates H2O and CO2 to generate electricity; SOEC module, the CO2 in the SOFC module enters the second fuel electrode of the SOEC module, and is electrolyzed at the second fuel electrode of the SOEC module to generate CO and O 2‑ , O 2‑ The electrons are lost at the second air electrode to obtain O2, which is supplied to the first air electrode; the CO generated by the second fuel electrode enters the reverse Boudouard reaction generating device, and a reverse Boudouard reaction occurs to generate CO2 and carbon black, the carbon black enters the SOFC module for gasification, and the generated CO2 enters the second fuel electrode as a raw material for making carbon black for electrolysis and / or enters the carbon layer as a carbon gasification medium. The closed cycle system of the present invention achieves efficient power generation in the process of producing carbon black.

Description

Technical Field

[0001] The present invention relates to the fields of chemical industry and power generation, and in particular to a system and method for combining CO2 reduction to produce carbon black and cyclic power generation. Background Art

[0002] Carbon black is a kind of amorphous carbon, light, loose and extremely fine black powder, existing in the form of colloidal particles similar to spheres and aggregates of colloidal size. The basic particle size is between 10-100nm, and the specific surface area is very large, ranging from 10-3000m 2 / g, with excellent rubber reinforcement, coloring, conductivity or antistatic and ultraviolet absorption functions, is the earliest nano-scale material developed and applied by humans. It can be divided into rubber carbon black, pigment carbon black, and conductive carbon black according to its use, and has a wide range of application space and utilization value.

[0003] Rubber carbon black is the most widely used carbon black at present. Rubber carbon black mainly plays a role of high wear resistance and reinforcement in rubber. Generally, the amount used in rubber accounts for between 20% and 70% of the raw rubber, and the amount used varies according to different rubber products.

[0004] Pigment carbon black can generally color plastics well. Pigment carbon black can be selected according to coloring characteristics or physical and chemical properties. The selection of coloring carbon black varieties is basically determined by the blackness that the finished product must achieve. Because pigment carbon black is a black pigment, it has a wide range of applications in the market.

[0005] Carbon black itself is a semiconductor material. Conductive carbon black has a low resistivity and can make rubber or plastic have certain conductivity. It is used in different conductive or antistatic products, such as antistatic or conductive rubber, plastic products, cable materials, and can also be used as raw materials for dry batteries.

[0006] Carbon black is usually produced by incomplete combustion or thermal cracking of hydrocarbon compounds (liquid or gaseous). Compared with hydrocarbon compounds, carbon dioxide is more widely available and has a lower cost of utilization. Therefore, the conversion of carbon dioxide to carbon black is a process with high practical application value and great development potential, but this process is difficult to achieve. CO2 has high thermal stability and its decomposition requires extremely high operating temperatures (greater than 2000K). In addition, the current reliance on solid heterogeneous catalysts means that the formation of solid carbon products usually leads to rapid deactivation of the catalyst due to coking. Therefore, the process of decomposing carbon dioxide to produce carbon is scarce, and the process mainly involves the conversion between chemical energy and thermal energy.

[0007] Reversible solid oxide cell (rSOC) system can realize the flexible interaction of heterogeneous energy in the electrochemical energy system and has broad development space. It consists of two modes: solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC). In the SOEC mode, the battery converts electrical energy into chemical energy and can achieve the purpose of compound conversion design; in the SOFC mode, the battery converts chemical energy into electrical energy to achieve an efficient power generation process.

[0008] Among them, compared with other electrolysis methods, solid oxide electrolysis cell (SOEC) has the advantages of all-solid state, high energy efficiency, fast reaction kinetics, strong flexibility and great potential. The basic gas distribution method is usually to introduce the reactants to be electrolyzed (CO2, H2O, etc.) into the fuel electrode and the purge gas (air, oxygen, etc.) into the air electrode. The efficiency of SOEC without heat recovery system is in the range of 90~120%.

[0009] Solid oxide fuel cell (SOFC) is an all-solid-state chemical power generation device that can directly convert chemical energy stored in fuel and oxidant into electrical energy in an efficient and environmentally friendly manner at medium and high temperatures. Compared with other types of fuel cells, solid oxide fuel cells have irreplaceable advantages such as all-solid-state structure, excellent reaction kinetics, no need for precious metal catalysts, and high fuel flexibility. Thanks to the high operating temperature (600~1000℃) and flexible catalyst selection, SOFC can use H2, CO, CH4, NH3, coal, biomass, waste organic matter and other substances as fuels, and the energy conversion efficiency of the system is in the range of 50-70%.

[0010] Coupling the thermochemical cycle process with the solid oxide battery can, in principle, realize the closed cycle of chemical substances and the efficient conversion between energies, which has great development potential. Currently, there have been many studies on the sulfur-iodine cycle, hybrid sulfur cycle, and the coupling between coal gasification and SOFC, but they all have problems such as difficulty in product separation and many side reactions (the control of reaction direction has strict requirements on catalysts). Summary of the invention

[0011] In view of the above problems, the present invention provides a combined system for producing carbon black by reducing CO2 and circulating power generation with easy product separation and few side reactions and an operation method. The system uses the CO2 generated by power generation from the carbon gasification product in the SOFC module as a raw material, electrolyzes the CO2 to obtain CO, and the CO undergoes a reverse Boudouard reaction to obtain carbon black and CO2. The produced carbon black can be gasified as a carbon source, the produced CO2 can be provided to the SOFC module and / or SOEC module, and the O2 produced by electrolysis can be provided to the SOFC module for power generation. Power generation is achieved in the process of producing carbon black, thereby realizing a closed cycle of chemical substances and efficient conversion between energies.

[0012] The present invention provides a combined system for producing carbon black by reducing CO2 and generating power by circulation, comprising: a SOFC module including a carbon layer, the carbon layer is gasified by water vapor and CO2 to produce fuel gas H2 and CO, O2 is introduced into the first air electrode of the SOFC module, and the O2 in the first air electrode is ionized to produce O 2- The fuel gas H2 and CO generated by carbon layer gasification are mixed with O from the first air electrode at the first fuel electrode of the SOFC module. 2- The reaction generates H2O and CO2 to generate electricity; SOEC module, the CO2 in the SOFC module enters the second fuel electrode of the SOEC module, and is electrolyzed at the second fuel electrode of the SOEC module to generate CO and O 2- , O produced by the second fuel electrode 2- The second air electrode of the SOEC module loses electrons to obtain O2, and the O2 produced by the second air electrode is supplied to the first air electrode; the CO produced by the second fuel electrode enters the reverse Boudouard reaction generating device, and a reverse Boudouard reaction occurs to produce CO2 and carbon black, and the carbon black enters the SOFC module as a carbon source for gasification, and the CO2 in the reverse Boudouard reaction generating device enters the second fuel electrode as a raw material for making carbon black for electrolysis and / or enters the carbon layer as a carbon gasification medium.

[0013] The present invention uses CO2 generated by power generation of SOFC module as raw material, and prepares carbon black by two-step reduction method. In the process of preparing carbon black, CO2 is electrolyzed to produce CO and O2, and the O2 generated by electrolysis is supplied to SOFC module. The CO generated by electrolysis undergoes reverse Boudouard reaction to produce carbon black and CO. 2，The generated carbon black can enter the SOFC module for gasification to produce fuel gas, and the generated CO2 can be used as the carbon gasification medium of the SOFC module and / or the electrolysis raw material of the SOEC module, so that the SOFC module can generate electricity continuously and stably, the SOEC module can perform electrolysis continuously and stably, and the reverse Boudouard reaction can be performed continuously and stably, realizing a closed-loop system for efficient power generation. The present invention supplements H2O as a carbon gasification medium, improves the carbon gasification efficiency, and thus improves the power generation efficiency. In the carbon black production process of the present invention, no organic matter is involved, the product categories are few, and it is easy to separate, and the carbon black is directly produced by a two-step method using CO2 as a raw material, without the use of a catalyst, saving costs while also avoiding the problem of rapid deactivation of the catalyst due to coking.

[0014] In the optional technical solution of the present invention, the SOFC module includes a carbon layer flow channel, a carbon layer, a first fuel electrode flow channel, a first fuel electrode, a first electrolyte, a first air electrode, a first air electrode flow channel and an electric energy output power supply for outputting electric energy to the outside, and the carbon gasification media water vapor and carbon dioxide are introduced into the first fuel electrode flow channel, and oxygen is introduced into the first air electrode flow channel.

[0015] According to the technical solution, the SOFC module has a simple structure and is easy to manufacture, which is beneficial to reducing system costs.

[0016] In an optional technical solution of the present invention, the flow rate of water vapor in the first fuel electrode and the flow rate of oxygen in the first air electrode flow channel are both 50-500 mL / min.

[0017] According to this technical solution, by controlling the oxygen flow rate within a reasonable range, it is possible to avoid heat loss in the SOFC module due to excessive air flow. By controlling water vapor within a reasonable range, it is possible to adjust the carbon gasification rate and maintain the CO concentration, thereby ensuring the power generation efficiency of the fuel gas and promoting the temperature-reliable operation of the combined system of CO2 reduction to produce carbon black and circulating power generation.

[0018] In an optional technical solution of the present invention, the reaction temperature of the SOFC module is 600-1000°C.

[0019] According to the technical solution, in this temperature range, the reaction rate of the carbon layer in the SOFC module with water vapor and CO2 is relatively high, which is beneficial to increasing the carbon gasification rate and improving the output performance of the SOFC module.

[0020] In an optional technical solution of the present invention, the SOFC module is a tubular cell.

[0021] According to this technical solution, the tubular cells are helpful to ensure the sealing of the SOFC module.

[0022] In an optional technical solution of the present invention, the SOEC module includes a second fuel electrode flow channel, a second fuel electrode, a second electrolyte, a second air electrode, a second air electrode flow channel, and an external power supply for supplying power to the second fuel electrode and the second air electrode. Carbon dioxide is introduced into the second fuel electrode, and air or water vapor is introduced into the second air electrode as a purge gas. The external power supply is fluctuating electric energy.

[0023] According to the technical solution, the SOEC module has a simple structure and is easy to manufacture, and uses fluctuating electric energy to provide the electric energy required for electrolysis, thereby improving the utilization rate of external electric energy and saving energy.

[0024] In an optional technical solution of the present invention, the flow rate of the fluid introduced into the second fuel electrode flow channel and the second air electrode flow channel is 50-500 mL / min.

[0025] According to this technical solution, by controlling the flow rate of the fluid in the second fuel electrode flow channel and the second air electrode flow channel, the concentration of CO2 in the SOEC module can be maintained and the electrolysis efficiency can be improved.

[0026] In an optional technical solution of the present invention, the reaction temperature of the SOEC module is 600-1000°C.

[0027] According to the technical solution, at this temperature, the electrochemical reaction rate is relatively fast, which is beneficial to improving the electrolysis efficiency, achieving a better match between the electrochemical rate and the carbon gasification rate, and improving the output performance of the SOFC module and the electrolysis rate of the SOEC module.

[0028] In an optional technical solution of the present invention, the operating temperature of the reverse Boudoir reaction generating device is 400-700°C.

[0029] According to the technical solution, the temperature required for the reverse Boudoir reaction is relatively low, and the two-step reduction method for producing carbon black reduces the temperature required for the system and reduces energy consumption.

[0030] The present invention further provides an operation method of the above-mentioned CO2 reduction carbon black production and cycle power generation combined system, comprising a carbon black preparation step and a power generation step, wherein the power generation step comprises: introducing carbon gasification media water vapor and CO2 into the carbon layer of the SOFC module, gasifying the carbon layer to produce fuel gas H2 and CO; introducing O2 into the first air electrode of the SOFC module, ionizing the O2 in the first air electrode to produce O 2- The fuel gas H2 and CO generated by the carbon layer gasification are in the first fuel electrode of the SOFC module and the O from the first air electrode 2- The reaction generates H2O and CO2 to generate electricity; the carbon black preparation step includes sub-steps: electrolysis step: the CO2 generated by the SOFC module is introduced into the second fuel electrode of the SOEC module, and the CO2 of the second fuel electrode is electrolyzed to generate CO and O 2-, O produced by the second fuel electrode 2- The second air electrode of the SOEC module loses electrons to obtain O2, and the O2 produced by the second air electrode is supplied to the first air electrode; the reverse Boudouard reaction step: the CO produced by electrolysis of the second fuel electrode is introduced into the reverse Boudouard reaction generating device, and the CO undergoes a reverse Boudouard reaction to produce CO2 and carbon black, and the carbon black enters the SOFC for gasification as a carbon source, and the CO2 in the reverse Boudouard reaction generating device is introduced into the second fuel electrode as a raw material for making carbon black for electrolysis and / or introduced into the carbon layer as a carbon gasification medium. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of the operation process of the combined system of CO2 reduction to produce carbon black and circulating power generation in an embodiment of the present invention.

[0032] Figure 2 Schematic diagram of the structure of the SOFC module in an embodiment of the present invention.

[0033] Figure 3 Schematic diagram of the structure of the SOEC module in an embodiment of the present invention.

[0034] Reference numerals:

[0035] SOFC module 1; carbon layer 11; first air electrode 12; first fuel electrode 13; carbon layer flow channel 14; carbon layer flow channel inlet 141; carbon layer flow channel outlet 142; first fuel electrode flow channel 15; first electrolyte 16; first air electrode flow channel 17; first air electrode flow channel inlet 171; first air electrode flow channel outlet 172; power output power supply 18; SOEC module 2; second fuel electrode 21; second air electrode 22; second fuel electrode flow channel 23; second fuel electrode flow channel inlet 231; second fuel electrode flow channel outlet 232; second electrolyte 24; second air electrode flow channel 25; second air electrode flow channel inlet 251; second air electrode flow channel outlet 252; external power supply 26; reverse Boudoir reaction generating device 3. DETAILED DESCRIPTION

[0036] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] See also Figure 1 , Figure 2 and Figure 3As shown, the present invention provides a combined system for producing carbon black by reducing CO2 and generating power by circulation, comprising: a SOFC module 1, comprising a carbon layer 11, the carbon layer 11 is gasified by water vapor and CO2 to produce fuel gas H2 and CO, a first air electrode 12 of the SOFC module 1 is introduced with O2, and the O2 in the first air electrode 12 is ionized to produce O 2- The fuel gas H2 and CO generated by gasification of the carbon layer 11 are mixed with the O from the first air electrode 12 at the first fuel electrode 13 of the SOFC module 1. 2- The reaction generates H2O and CO2 to generate electricity; SOEC module 2, CO2 in SOFC module 1 enters the second fuel electrode 21 of SOEC module 2, and is electrolyzed at the second fuel electrode 21 of SOEC module 2 to generate CO and O 2- , O produced by the second fuel electrode 21 2- The second air electrode 22 of the SOEC module 2 loses electrons to obtain O2, and the O2 generated by the second air electrode 22 is supplied to the first air electrode 12; the CO generated by the reverse Boudoir reaction generating device 3, the second fuel electrode 21 enters the reverse Boudoir reaction generating device 3, and a reverse Boudoir reaction occurs to generate CO2 and carbon black, and the carbon black enters the SOFC module 1 as a carbon source for gasification, and the CO2 in the reverse Boudoir reaction generating device 3 enters the second fuel electrode 21 as a raw material for making carbon black for electrolysis and / or enters the carbon layer 11 as a carbon gasification medium.

[0038] The present invention uses CO2 generated by power generation of SOFC module 1 as raw material, and prepares carbon black by two-step reduction method. In the process of preparing carbon black, CO2 is electrolyzed to produce CO and O2, and the O2 generated by electrolysis is supplied to SOFC module 1. The CO generated by electrolysis undergoes reverse Boudouard reaction to produce carbon black and CO. 2， The generated carbon black can enter the SOFC module 1 for gasification to produce fuel gas, and the generated CO2 can be used as the carbon gasification medium of the SOFC module 1 and / or the electrolysis raw material of the SOEC module 2, so that the SOFC module 1 can generate electricity continuously and stably, the SOEC module 2 can perform electrolysis continuously and stably, and the reverse Boudouard reaction can be performed continuously and stably, realizing a closed-loop system for efficient power generation. The present invention supplements H2O as a carbon gasification medium, improves the carbon gasification efficiency, and thus improves the power generation efficiency. In the carbon black production process of the present invention, no organic matter is involved, the product categories are few, and it is easy to separate, and the carbon black is produced directly by a two-step method using CO2 as a raw material, without the use of a catalyst, saving costs while also avoiding the problem of rapid deactivation of the catalyst due to coking.

[0039] Specifically, if Figure 2As shown, the SOFC module 1 includes a carbon layer flow channel 14, a carbon layer 11, a first fuel electrode flow channel 15, a first fuel electrode 13, a first electrolyte 16, a first air electrode 12, a first air electrode flow channel 17, and an electric energy output power supply 18 for outputting electric energy to the outside, and water vapor, a carbon gasification medium, is introduced into the first fuel electrode flow channel 15, and oxygen is introduced into the first air electrode flow channel 12. In the embodiment of the present invention, the SOFC module 1 has a simple structure and is easy to manufacture, which is conducive to reducing system costs.

[0040] When SOFC module 1 is working, the reaction equation is as follows:

[0041] Carbon layer 11: C+H2O→CO+H2

[0042] C+CO2→2CO

[0043] First fuel electrode 13 (anode): CO-2e - +O 2- →CO2

[0044] H2-2e - +O 2- →H2O

[0045] First air electrode 12 (cathode): O2+2e - →2O 2-

[0046] Oxygen is reduced to O in the first air electrode 2- , the generated O 2- The carbon monoxide is transported to the first fuel electrode 13 through the first electrolyte, combines with the hydrogen and carbon monoxide in the first fuel electrode 13, and undergoes an oxidation reaction to generate water and carbon dioxide.

[0047] In a preferred embodiment of the present invention, the flow rate of water vapor in the first fuel electrode 13 and the flow rate of oxygen in the first air electrode flow channel are both 50-500 mL / min.

[0048] Through the above method, by controlling the oxygen flow rate within a reasonable range, it is possible to avoid heat loss in the SOFC module 1 due to excessive air flow. By controlling the water vapor within a reasonable range, the carbon gasification rate can be adjusted and the CO concentration can be maintained to ensure the power generation efficiency of the fuel gas and promote the temperature-reliable operation of the CO2 reduction to carbon black and cycle power generation combined system.

[0049] In a preferred embodiment of the present invention, the reaction temperature of the SOFC module 1 is 600-1000°C.

[0050] Through the above method, in this temperature range, the reaction rate of the carbon layer 11 in the SOFC module 1 with water vapor and CO 2 is relatively high, which is beneficial to improving the carbon gasification rate and improving the output performance of the SOFC module 1 .

[0051] In a preferred embodiment of the present invention, the SOFC module 1 is a tubular cell.

[0052] In the above manner, the tubular cell is helpful to ensure the sealing of the SOFC module 1; in some embodiments, the SOFC module 1 may also be a flat cell, and the embodiment of the present invention does not limit the specific form of the SOFC module 1.

[0053] In a preferred embodiment of the present invention, Figure 3 As shown, the SOEC module 2 includes a second fuel electrode flow channel 23, a second fuel electrode 21, a second electrolyte 24, a second air electrode 22, a second air electrode flow channel 25, and an external power source 26 for supplying power to the second fuel electrode 21 and the second air electrode 22. Carbon dioxide is introduced into the second fuel electrode 21, and air or water vapor is introduced into the second air electrode 22 as a purge gas. The external power source 26 is fluctuating electric energy. In the embodiment of the present invention, the SOEC module 2 has a simple structure and is easy to manufacture. The use of fluctuating electric energy to provide the electric energy required for electrolysis improves the utilization rate of external electric energy and saves energy. When the SOEC module 2 is working, the reaction formula is as follows:

[0054] Second fuel electrode 21 (cathode): CO2+2e - →CO+O 2- ;

[0055] Second air electrode 22 (anode): O 2- -2e - →0.5O2;

[0056] The carbon dioxide is reduced to carbon monoxide at the second fuel electrode 21, and O 2- , O 2- The oxygen is transported to the second air electrode 22 through the second electrolyte, oxidized in the second air electrode 22 to generate oxygen, and the generated oxygen is swept and carried out by the air introduced from the inlet of the second air electrode flow channel 25.

[0057] In a preferred embodiment of the present invention, the flow rate of the fluid flowing into the second fuel electrode flow channel 23 and the second air electrode flow channel 25 is 50-500 mL / min.

[0058] In the above manner, by controlling the flow rate of the fluid in the second fuel electrode flow channel 23 and the second air electrode flow channel 25, the concentration of CO2 in the SOEC module 2 can be maintained and the electrolysis efficiency can be improved.

[0059] In a preferred embodiment of the present invention, the reaction temperature of the SOEC module 2 is 600-1000°C.

[0060] Through the above method, at this temperature, the electrochemical reaction rate is faster, which is beneficial to improving the electrolysis efficiency, achieving a better match between the electrochemical rate and the carbon gasification rate, and improving the output performance of the SOFC module 1 and the electrolysis rate of the SOEC module 2.

[0061] In a preferred embodiment of the present invention, the operating temperature of the reverse Boudoir reaction generating device 3 is 400-700°C.

[0062] Through the above method, the temperature required for the reverse Boudoir reaction is low, and the two-step reduction method for producing carbon black reduces the temperature required for the system and reduces energy consumption.

[0063] In a preferred embodiment of the present invention, the material used for the first fuel electrode 13 and the second fuel electrode 21 is a composite nickel-yttrium stabilized zirconia, the first electrolyte 16 and the second electrolyte 24 are yttrium stabilized zirconia / samarium-doped cerium oxide double-layer electrolytes, and the material used for the first air electrode 12 and the second air electrode 22 is a lanthanum strontium cobalt ferrite material.

[0064] Corresponding to the above-mentioned CO2 reduction to carbon black and cyclic power generation combined system, the present invention further provides an operation method of the above-mentioned CO2 reduction to carbon black and cyclic power generation combined system, including a carbon black preparation step and a power generation step, wherein:

[0065] The power generation step includes: introducing carbon gasification media water vapor and CO2 into the carbon layer 11 of the SOFC module 1, and the carbon layer 11 is gasified to produce fuel gas H2 and CO; introducing O2 into the first air electrode of the SOFC module 1, and the O2 in the first air electrode is ionized to produce O 2- The fuel gas H2 and CO generated by gasification of the carbon layer 11 are in the first fuel electrode 13 of the SOFC module 1 and the O from the first air electrode 12 2- The reaction generates H2O and CO2 to generate electricity;

[0066] The carbon black preparation step includes the following sub-steps:

[0067] Electrolysis step: CO2 generated by SOFC module 1 is introduced into the second fuel electrode 21 of SOEC module 2, and CO2 in the second fuel electrode 21 is electrolyzed to produce CO and O 2- , O produced by the second fuel electrode 21 2- The second air electrode 22 of the SOEC module 2 loses electrons to obtain O2, and the O2 generated by the second air electrode 22 is supplied to the first air electrode 12;

[0068] Reverse Boudouard reaction step: the CO generated by electrolysis of the second fuel electrode 21 is introduced into the reverse Boudouard reaction generating device 3, the CO undergoes a reverse Boudouard reaction to produce CO2 and carbon black, the carbon black enters the SOFC module 1 as a carbon source for gasification, the CO2 in the reverse Boudouard reaction generating device 3 is introduced into the second fuel electrode 21 as a raw material for making carbon black for electrolysis and / or introduced into the carbon layer 11 as a carbon gasification medium.

[0069] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A combined system of CO2 reduction to produce carbon black and circulating power generation, characterized in that: include: The SOFC module comprises a carbon layer, wherein the carbon layer is gasified by water vapor and CO2 to produce fuel gas H2 and CO, and the first air electrode of the SOFC module is introduced with O2, and the O2 of the first air electrode is ionized to produce O 2- The fuel gas H2 and CO generated by gasification of the carbon layer are mixed with O from the first air electrode of the SOFC module at the first fuel electrode. 2- The reaction generates H2O and CO2 to generate electricity; The CO2 in the SOFC module enters the second fuel electrode of the SOEC module and is electrolyzed at the second fuel electrode of the SOEC module to generate CO and O 2- , the second fuel electrode produces O 2- The second air electrode of the SOEC module loses electrons to obtain O2, and the O2 generated by the second air electrode is supplied to the first air electrode; A reverse Boudouard reaction generating device, wherein the CO generated by the second fuel electrode enters the reverse Boudouard reaction generating device and undergoes a reverse Boudouard reaction to generate CO2 and carbon black, wherein the carbon black enters the SOFC module as a carbon source for gasification, and the CO2 in the reverse Boudouard reaction generating device enters the second fuel electrode as a raw material for making carbon black for electrolysis and / or enters the carbon layer as a carbon gasification medium.

2. The CO2 reduction to carbon black and cycle power generation combined system according to claim 1 is characterized in that: The SOFC module includes a carbon layer flow channel, the carbon layer, a first fuel electrode flow channel, the first fuel electrode, a first electrolyte, the first air electrode, a first air electrode flow channel and an electric energy output power supply for outputting electric energy to the outside, wherein the carbon gasifying substances water vapor and carbon dioxide are introduced into the first fuel electrode flow channel, and oxygen is introduced into the first air electrode flow channel.

3. The CO2 reduction to carbon black and cycle power generation combined system according to claim 2 is characterized in that: The flow rate of water vapor in the first fuel electrode and the flow rate of oxygen in the first air electrode flow channel are both 50-500 mL / min.

4. The CO2 reduction to carbon black and cycle power generation combined system according to claim 1 is characterized in that: The reaction temperature of the SOFC module is 600-1000°C.

5. The CO2 reduction to carbon black and cycle power generation combined system according to claim 1 is characterized in that: The SOFC module is a tubular cell.

6. The CO2 reduction to carbon black and cycle power generation combined system according to claim 1 is characterized in that: The SOEC module includes a second fuel electrode flow channel, the second fuel electrode, a second electrolyte, the second air electrode, a second air electrode flow channel, and an external power supply for supplying power to the second fuel electrode and the second air electrode, wherein carbon dioxide is introduced into the second fuel electrode, and air or water vapor is introduced into the second air electrode as a purge gas, and the external power supply is fluctuating electric energy.

7. The CO2 reduction to carbon black and cycle power generation combined system according to claim 6 is characterized in that: The flow rates of the fluid flowing into the second fuel electrode flow channel and the second air electrode flow channel are both 50-500 mL / min.

8. The CO2 reduction to carbon black and cycle power generation combined system according to claim 6 is characterized in that: The reaction temperature of the SOEC module is 600-1000°C.

9. The CO2 reduction to carbon black and cycle power generation combined system according to claim 1 is characterized in that: The operating temperature of the reverse Boudoir reaction generating device is 400-700°C.

10. A method for operating a combined system of CO2 reduction to produce carbon black and circulating power generation as claimed in any one of claims 1 to 9, characterized in that: The method comprises a carbon black preparation step and a power generation step, wherein: The power generation step includes: introducing carbon gasification media water vapor and CO2 into the carbon layer of the SOFC module, and gasifying the carbon layer to produce fuel gas H2 and CO; O2 is introduced into the first air electrode of the SOFC module, and the O2 in the first air electrode is ionized to generate O 2- ; The fuel gas H2 and CO generated by gasification of the carbon layer are mixed with O from the first air electrode of the SOFC module at the first fuel electrode. 2- The reaction generates H2O and CO2 to generate electricity; The carbon black preparation step comprises the following sub-steps: Electrolysis step: passing the CO2 generated by the SOFC module into the second fuel electrode of the SOEC module, and electrolyzing the CO2 of the second fuel electrode to produce CO and O 2- , the second fuel electrode produces O 2- The second air electrode of the SOEC module loses electrons to obtain O2, and the O2 generated by the second air electrode is supplied to the first air electrode; Reverse Boudouard reaction step: the CO generated by the electrolysis of the second fuel electrode is introduced into the reverse Boudouard reaction generating device, the CO undergoes a reverse Boudouard reaction to produce CO2 and carbon black, the carbon black enters the SOFC as a carbon source for gasification, the CO2 in the reverse Boudouard reaction generating device is introduced into the second fuel electrode as a raw material for making carbon black for electrolysis and / or introduced into the carbon layer as a carbon gasification medium.

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