Sulfur and carbon integrated removal system and method

Abstract

The invention discloses a sulfur-carbon integrated removal system and method, and belongs to the field of electrochemistry, the sulfur-carbon integrated removal system driven by proton circulation is constructed by competitively replacing anode electrochemical SO2 oxidation reaction through an organic matter electric coupling agent and combining electrochemical carbon dioxide reduction, and the system is used for deeply recovering low-grade SO2 oxidation reaction energy; cO2 electrochemical reduction is realized, and the electrolysis energy consumption in the whole process is reduced. According to the method, separation of SO2 chemical oxidation reaction and CO2 electrochemical reduction reaction in time and space is completed in principle in a spatial decoupling mode, the problem of CO2 catalyst poisoning caused by SO2 entering an electrochemical system is avoided, extra consumption of a electrochemical coupling agent is not needed, stable separation of sulfuric acid with lower cost and higher efficiency is facilitated, and the method is suitable for industrial production. And the design field of fossil energy clean utilization devices in the future is facilitated.

Description

Technical Field

[0001] The present invention relates to the field of electrochemistry, and more specifically, to a sulfur-carbon integrated removal system and method. Background Art

[0002] Global industrialization has led to a massive consumption of fossil energy. my country's energy structure, which is dominated by coal, will not undergo fundamental changes in the short term. The problems of flue gas pollution (SO2) and low carbon emissions (CO2) caused by coal combustion are becoming increasingly serious.

[0003] In order to meet future demand, coal-fired power plants need to use carbon capture, storage and utilization (CCUS) technology to achieve low carbon emissions. The CCUS equipment currently in operation in China generally has problems such as high capture cost and limited product utilization. In addition, existing flue gas desulfurization technologies such as wet lime\limestone-gypsum method, double alkali method and carbon-based catalytic method also have disadvantages such as high energy consumption and high cost. Therefore, the development of integrated sulfur and carbon removal technology is an effective way to solve the dilemma of low-carbon desulfurization emissions in coal-fired power. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an integrated sulfur-carbon removal system and method, which can utilize solar photovoltaic units to independently obtain renewable energy, and capture the flue gas and waste gas generated by the combustion of fossil fuels through electrochemical means and convert them into chemical raw materials with high added value, which will play an important role in realizing the low-carbon and desulfurization comprehensive utilization of traditional energy sources such as coal and fuel oil in the future.

[0005] The object of the present invention is achieved through the following solutions:

[0006] A sulfur-carbon integrated removal system, comprising: an electrolysis system, a renewable energy power generation device, a UPS rectifier, a power supply, a first valve, a cathode liquid storage tank, a first liquid pump, a second liquid pump, a second valve, an anode reaction zone, a cathode reaction zone, a third liquid pump, a third valve, a gas-liquid separator, a liquid product collecting device, a gas dryer, a gas product collecting device, an extraction device, an HSO collecting device, a fourth valve, a fifth valve, an anode liquid storage tank, a fourth liquid pump and a reduction tower;

[0007] The electric energy of the power supply can be provided by a renewable energy power generation device after being processed by a UPS rectifier;

[0008] The electrolysis system is connected to a power supply through a wire; an anode reaction zone is provided on one side of the electrolysis system, and a cathode reaction zone is provided on the other side; the anode reaction zone and the cathode reaction zone are separated by a proton exchange membrane; the cathode reaction zone of the electrolysis system is connected to the liquid inlet of the cathode liquid storage tank through a liquid infusion tube through a first valve, the bottom end of the cathode liquid storage tank is connected to the first liquid pump through a liquid infusion tube, and the liquid outlet of the first liquid pump is connected to the cathode reaction zone of the electrolysis system through a liquid infusion tube;

[0009] The cathode liquid storage tank is connected to the third liquid pump through a liquid infusion tube, and the liquid outlet of the third liquid pump is connected to the gas-liquid separator through a liquid infusion tube; the side end of the gas-liquid separator is connected to the cathode liquid storage tank through a liquid infusion tube through a third valve; the lower end of the gas-liquid separator is connected to the liquid product collection device through a liquid infusion tube; the top end of the gas-liquid separator is connected to the gas dryer through a gas delivery tube, and the outlet of the gas dryer is connected to the gas product collection device through the gas delivery tube;

[0010] The anode reaction zone of the electrolysis system is connected to the liquid inlet of the anode liquid storage tank through a liquid infusion tube via a second valve, the bottom end of the anode liquid storage tank is connected to the second liquid pump through a liquid infusion tube, and the liquid outlet of the second liquid pump is connected to the anode reaction zone of the electrolysis system through a liquid infusion tube;

[0011] The anode liquid storage tank is connected to the fourth liquid pump through a liquid infusion tube, the liquid outlet of the fourth liquid pump is connected to the reduction tower through a liquid infusion tube, and the lower end of the reduction tower is connected to the anode liquid storage tank through a liquid infusion tube through a fourth valve;

[0012] The anode liquid storage tank is connected to the extraction device through a liquid infusion tube via a fifth valve, and a side liquid outlet of the extraction device is connected to the anode liquid storage tank through a liquid infusion tube.

[0013] Furthermore, the liquid outlet at the bottom of the extraction device is connected to the HSO collection device through an infusion tube.

[0014] Furthermore, the interior of the cathode reaction zone is filled with NaHCO3 solution.

[0015] Furthermore, a solution containing an organic electrical coupling agent Q is provided inside the anode reaction zone, and the types of the organic electrical coupling agent Q include AQDS, ADS, BQDS, Fe(CN)63- / 4-, MDEA, Tiron, TironA and its derivatives, phenol and its derivatives, phenothiazine derivatives and ferrocene derivatives or organic matter with PCET electrochemical reaction activity.

[0016] Furthermore, the reduction tower is provided with a catalyst capable of catalyzing the reaction of SO2 and an organic electric coupling agent, including a platinum catalyst, a palladium catalyst, V / Al2O3, graphite, activated carbon, a gold catalyst, RuO2, WO3 and a substance capable of catalyzing the oxidation reaction of SO2.

[0017] Furthermore, the cathode reaction zone () is provided with a catalyst capable of catalyzing CO reduction reaction, including Ag, Fe, Cu-based catalysts, cobalt phthalocyanine, nickel phthalocyanine and a catalyst capable of catalyzing CORR reaction.

[0018] A sulfur-carbon integrated removal method comprises the following steps:

[0019] S, constructing the sulfur-carbon integrated removal system as described above;

[0020] S, organic matter coupling agent QH undergoes oxidation reaction in the anode reaction zone of the electrolysis system to Q and releases protons H + , the solution enters the reduction tower through the second valve under the action of the fourth pumping pump to react with SO to generate QH and sulfuric acid, QH returns to the anode reaction zone under the action of the second pumping pump to complete the cycle, the solution in the anode storage tank is collected to the HSO collection device through the extraction device, the protons generated by the anode reaction reach the cathode reaction zone through the proton exchange membrane to react with CO under the action of the catalyst to produce CO reduction reaction, the reacted solution reaches the gas-liquid separator through the first valve under the action of the third pumping pump, the gas product enters the gas product collection device through the gas drying tube, and the liquid product enters the liquid product collection device; the self-reduction semi-decoupled sulfur-carbon integrated removal system constructed by the above steps can realize sulfur-carbon integrated removal, and the overall reaction formula of the whole system is:

[0021] CO2+4SO4+6H20=CH4+4H2SO4.

[0022] The beneficial effects of the present invention include:

[0023] The present invention proposes a novel proton cycle-driven integrated sulfur-carbon removal strategy, and designs an integrated sulfur-carbon removal electrochemical system. Among them, the system of the present invention is driven by electric energy provided by renewable energy, and an organic electric coupling agent with PCET electrochemical reaction activity is used as a medium. According to the reaction principle of PCET, the CO2 electrochemical reduction reaction and the SO2 oxidation reaction are separated in time and space, so as to produce high-value products while removing sulfur and carbon in an integrated manner. Specifically, the novel integrated sulfur-carbon removal system of the present invention realizes the integrated removal of sulfur and carbon through three main processes: power generation by solar photovoltaic units, electrochemical reduction of CO2, and chemical oxidation of SO2 to generate H2SO4. The organic electric coupling agent circulates between the anode side of the electrolytic cell and a separate reactor. In the electrolytic cell, the CO2 electrochemical reduction reaction (CO2RR) occurs at the cathode, and the electrochemical oxidation reaction of the organic electric coupling medium occurs at the anode. The oxidized medium is transported to the external reduction reaction tower through circulation, and reacts with SO2 under the action of a catalyst to achieve chemical reduction regeneration. SO2 is oxidized to H2SO4, and excess sulfuric acid is obtained by extraction. Taking the reduction to form methane as an example, the overall reaction formula is CO2+4SO2+6H20=CH4+4H2SO4.

[0024] The present invention proposes a novel electrochemical system for integrated sulfur and carbon removal. By using organic electric coupling agents to compete with each other to replace the electrochemical SO2 oxidation reaction at the anode, combined with electrochemical carbon dioxide reduction (CO2RR) technology, a proton cycle-driven electrochemical sulfur and carbon integrated removal technology and system is constructed to deeply recover the energy of low-grade SO2 oxidation reaction, realize CO2 electrochemical reduction, and reduce the electrolysis energy consumption of the overall process. By using the redox principle, the electrochemical oxidation reaction of organic electric coupling agents is substituted for the electrochemical oxidation reaction of SO2. At the same time, the organic electric coupling agents are spontaneously chemically reduced under the action of catalysts, separating the SO2 oxidation reaction and the CO2 reduction reaction from the time scale and space scale, eliminating the risk of SO2 entering the electrochemical system and causing catalyst poisoning. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0026] Figure 1 It is a schematic diagram of the structure of the system of the embodiment of the present invention;

[0027] In the figure, 1-electrolysis system, 2-renewable energy power generation device, 3-UPS rectifier, 4-power supply, 5-first valve, 6-cathode liquid storage tank, 7-first liquid pump, 8-second liquid pump, 9-second valve, 10-anode reaction zone, 11-cathode reaction zone, 12-third liquid pump, 13-third valve, 14-gas-liquid separator, 15-liquid product collecting device, 16-gas dryer, 17-gas product collecting device, 18-extraction device, 19-H2SO4 collecting device, 20-fourth valve, 21-fifth valve, 22-anode liquid storage tank, 23-fourth liquid pump, 24-reduction tower.

[0028] Figure 2 This is a schematic diagram of the SOR high current density stability on the anode side of the system according to an embodiment of the present invention;

[0029] Figure 3 Schematic diagram of CO2 reduction stability on the cathode side of the system according to an embodiment of the present invention. DETAILED DESCRIPTION

[0030] All features disclosed in all embodiments in this specification, or steps in all methods or processes implicitly disclosed, except for mutually exclusive features and / or steps, can be combined and / or expanded or replaced in any manner.

[0031] In view of the problems in the background, the inventors of the present invention believe that:

[0032] As a substance with important reducing properties, SO2 contains rich chemical energy and can be oxidized to generate sulfuric acid at a relatively low potential of 0.158V vs RHE. In addition, CO2 is a non-toxic, cheap and abundant carbon source that can be reduced to high-value products such as methanol and methane. Using the advantages of SO2 and CO2 for targeted treatment, introducing indirect SO2 oxidation and CO2 electroreduction as the electrolysis system, and realizing the integrated removal of sulfur and carbon while converting them into high-value-added products will be an effective strategy to solve the problems in the background.

[0033] Therefore, the present invention aims to propose an electrolysis system combined with proton-coupled electron transfer (PCET). By introducing an organic electrical coupling agent as a medium, the SO2 oxidation reaction is separated from the electrochemical process. At the same time, the energy released by SO2 oxidation is used to promote the low-energy carbon dioxide electroreduction process CO2RR, thereby constructing an electrochemical sulfur-carbon integrated removal system, which can achieve low-energy, high-efficiency and stable sulfur-carbon integrated removal.

[0034] Specifically, photovoltaic or wind power provides renewable electricity, which is transmitted to the power supply through the UPS rectifier. Driven by renewable electricity, the cathode area of ​​the electrolysis system undergoes a carbon dioxide electrochemical reduction reaction CO2RR. Under the action of a specific catalyst, carbon dioxide CO2 is reduced to high value-added products such as methane CH4, carbon monoxide CO, methanol CH3OH, and formic acid HCOOH. Further gas-liquid separation and gas drying are performed to obtain gas and liquid products. At the same time, the anode area undergoes a PCET electrochemical oxidation reaction of an organic matter coupling agent to release protons H + , protons are transferred to the cathode side through the proton exchange membrane for electrocatalytic CO2 reduction; the oxidized organic matter electrical coupling agent is circulated to the external buffer tank through a pump, and the buffer tank solution is circulated to the reduction reaction tower through a pump, where it reacts with sulfur dioxide SO2 in the reduction reaction tower to be chemically reduced and regenerated, and SO2 is oxidized to sulfuric acid H2SO4, and then further passes through the extraction tower to collect the sulfuric acid product.

[0035] Taking the reduction of CO2 to methane as an example, the reaction equation is as follows:

[0036] Cathode area: CO2+8H + +8e - →CH4+2H2O

[0037] Anode area: QH2-2e - →Q+2H +

[0038] Chemical reaction zone: Q+SO2+2H2O→QH2+SO4 2- +2H +

[0039] Overall reaction: CO2+4SO2+6H2O→CH4+4H2SO4

[0040] The integrated sulfur-carbon removal system of the embodiment of the present invention can, in principle, separate the SO2 chemical oxidation reaction and the CO2 electrochemical reduction reaction in time and space by means of spatial decoupling, thereby avoiding the problem of SO2 entering the electrochemical system and causing CO2 catalyst poisoning. It does not require additional consumption of mass-electrochemical coupling agents, and is conducive to achieving lower-cost and more efficient stable separation of sulfuric acid, which will help to gain an advantage in the field of devices for the clean utilization of fossil energy in the future.

[0041] In a further embodiment, in combination Figure 1 The detailed description is as follows:

[0042] An embodiment of the present invention provides an integrated sulfur-carbon removal system, including an electrolysis system 1 for electrolysis, a renewable energy power generation device 2, a UPS rectifier 3, a power supply 4, a first valve 5, a cathode liquid storage tank 6, a first liquid pump 7, a second liquid pump 8, a second valve 9, an anode reaction zone 10, a cathode reaction zone 11, a third liquid pump 12, a third valve 13, a gas-liquid separator 14, a liquid product collecting device 15, a gas dryer 16, a gas product collecting device 17, an extraction device 18, an H2SO4 collecting device 19, a fourth valve 20, a fifth valve 21, an anode liquid storage tank 22, a fourth liquid pump 23, and a reduction tower 24.

[0043] The electrolysis system 1 is connected to a power source 4 for power supply via a wire, and the electric energy of the power source 4 is provided by a renewable energy power generation device 2 after being processed by a UPS rectifier 3 .

[0044] An anode reaction zone 10 is disposed on one side of the electrolysis system 1 , and a cathode reaction zone 11 is disposed on the other side. The anode reaction zone 10 and the cathode reaction zone 11 are separated by a proton exchange membrane.

[0045] The cathode reaction zone 11 of the electrolysis system 1 is connected to the liquid inlet of the cathode liquid storage tank 6 through the infusion tube through the first valve 5, the bottom end of the cathode liquid storage tank 6 is connected to the first liquid pump 7 through the infusion tube, and the liquid outlet of the first liquid pump 7 is connected to the cathode reaction zone 11 of the electrolysis system 1 through the infusion tube.

[0046] The cathode liquid storage tank 6 is connected to the third liquid pump 12 through a liquid infusion tube, and the liquid outlet of the third liquid pump 12 is connected to the gas-liquid separator 14 through a liquid infusion tube. The side end of the gas-liquid separator 14 is connected to the cathode liquid storage tank 6 through a liquid infusion tube through a third valve 13. The lower end of the gas-liquid separator 14 is connected to the liquid product collection device 15 through a liquid infusion tube. The top end of the gas-liquid separator 14 is connected to the gas dryer 16 through a gas delivery pipe, and the outlet of the gas dryer 16 is connected to the gas product collection device 17 through a gas delivery pipe.

[0047] The anode reaction zone 10 of the electrolysis system 1 is connected to the liquid inlet of the anode liquid storage tank 22 through an infusion tube via the second valve 9, the bottom end of the anode liquid storage tank 22 is connected to the second liquid pump 8 through an infusion tube, and the liquid outlet of the second liquid pump 8 is connected to the anode reaction zone 10 of the electrolysis system 1 through an infusion tube.

[0048] The anode liquid storage tank 22 is connected to the fourth liquid pump 23 through a liquid infusion tube, the liquid outlet of the fourth liquid pump 23 is connected to the reduction tower 24 through a liquid infusion tube, and the lower end of the reduction tower 24 is connected to the anode liquid storage tank 22 through a liquid infusion tube through the fourth valve 20.

[0049] The anode liquid storage tank 22 is connected to the extraction device 18 through a liquid infusion tube via the fifth valve 21, and the side liquid outlet of the extraction device is connected to the anode liquid storage tank 22 through a liquid infusion tube.

[0050] The liquid outlet at the bottom of the extraction device is connected to the H2SO4 collecting device 19 through a liquid infusion tube.

[0051] The interior of the cathode reaction zone 11 is filled with a NaHCO 3 solution.

[0052] An acidic solution containing an organic electrical coupling agent is disposed inside the anode reaction zone 10 .

[0053] The interior of the reduction tower 24 is provided with substances capable of catalyzing the reaction between SO2 and organic electrical coupling agents, including platinum catalysts such as platinum carbon, palladium catalysts such as palladium carbon, V / Al2O3, graphite, activated carbon, gold catalysts, RuO2, WO3 and other material catalysts capable of catalyzing the SO2 oxidation reaction.

[0054] In a further embodiment, a corresponding sulfur-carbon integrated removal method is provided, comprising the following steps:

[0055] The organic electric coupling agent is required to be a type of highly soluble redox couple that can undergo reversible redox, characterized by excellent redox cycling ability, strong stability in dilute sulfuric acid, and a theoretical redox potential (0.158V vs. RHE) slightly higher than the theoretical potential of SO2 oxidation reaction, but still lower than the actual potential of SO2 generation on the electrode material. The organic electric coupling agent Q also includes but is not limited to organic electric coupling agents Q including AQDS, ADS, BQDS, Fe(CN)63- / 4-, MDEA, Tiron, TironA and its derivatives, phenol and its derivatives, phenothiazine derivatives and ferrocene derivatives or organic substances with PCET electrochemical reaction activity.

[0056] In the system of this embodiment, AQDS / AQDSH2 is used as a mass-to-electrode coupling agent. This substance has good redox properties and is soluble in dilute sulfuric acid, meeting the basic requirements of a mass-to-electrode coupling agent. AQDS / AQDSH2 redox couple is used as a mass-to-electrode coupling agent and is used as a carrier circulating between the anode cell and a separate reactor to construct a self-reduction semi-decoupled sulfur-carbon integrated removal system to achieve sulfur-carbon integrated removal.

[0057] The mass-to-electrode coupling agent AQDSH2 is dissolved in dilute sulfuric acid and undergoes oxidation reaction in the anode reaction zone 10 of the electrolytic cell to form AQDS. The solution enters the anode liquid storage tank 22 through the second valve 9:

[0058] AQDSH2-2e - =2H + +AQDS

[0059] The solution in the anode liquid storage tank 22 enters the reduction tower 24 through the fourth liquid pump 23 and the liquid infusion pipe. AQDS undergoes a spontaneous redox reaction with SO2 under the action of the catalyst to produce AQDSH2 and H2SO4. The solution returns to the anode liquid storage tank 22 through the fourth valve 20:

[0060] AQDS+SO2+2H2O=H2SO4+AQDSH2

[0061] The solution in the anode liquid storage tank 22 is returned to the anode reaction area 10 through the second liquid pump 8 and the liquid infusion tube, thereby completing the stable circulation of the mass-to-electric coupling agent.

[0062] In a further embodiment, a corresponding sulfur-carbon integrated removal method is provided, comprising the following steps:

[0063] The cathode reaction zone 11 undergoes a CO2 electrochemical reduction reaction under the catalytic action of a specific catalyst. The design requirements of the catalyst are: the CO2 electrochemical reduction reaction CO2RR catalyzed by the catalyst has high selectivity, good activity and stability. Cobalt phthalocyanine is selected as the catalyst for the cathode carbon dioxide reduction reaction to meet the above requirements for the catalyst for the cathode reaction. The cathode reaction zone 11 undergoes the following reaction, and the solution enters the cathode liquid storage tank 6 through the first valve 5:

[0064] CO2+8H + +8e - =CH4+2H2O

[0065] The solution in the cathode liquid storage tank 6 enters the gas-liquid separator 14 through the third pumping pump 12, and the separated gas enters the gas product collecting device 17 through the gas pipe and the gas drying pipe 16. The separated liquid can return to the cathode liquid storage tank 6 through the third valve 13, and can also be transported to the liquid product collecting device 15 through the liquid pipe. The solution in the cathode liquid storage tank 6 returns to the cathode reaction zone 11 through the first pumping pump 7.

[0066] The overall reaction equation of the whole system is:

[0067] CO2+4SO4+6H20=CH4+4H2SO4.

[0068] In summary, the present invention has the following advantages:

[0069] Figure 2 This is a schematic diagram of the SOR high current density stability on the anode side of the system according to an embodiment of the present invention; Figure 3 Schematic diagram of CO2 reduction stability on the cathode side of the system according to an embodiment of the present invention.

[0070] The present invention innovatively combines the proton cycle-driven decoupling system with the sulfur and carbon removal from fossil fuel flue gas to construct an electrochemical sulfur and carbon integrated removal technology and system. It uses organic electrical coupling agents as redox media to couple the SO2 oxidation reaction and the CO2 electrochemical reduction into one system to achieve integrated sulfur and carbon removal.

[0071] The sulfur-carbon removal process driven by proton circulation of the present invention is as follows: the mass-to-electrode coupling agent undergoes an oxidation reaction in the anode reaction zone of the electrolytic cell, and the oxidized mass-to-electrode coupling agent is circulated and transferred to the reduction tower to undergo a spontaneous oxidation-reduction reaction with SO2 under the action of a catalyst, thereby realizing a reversible cycle of the mass-to-electrode coupling agent and producing H2SO4; a reduction reaction of CO2 occurs in the cathode reaction zone of the electrolytic cell, and CH4 is produced under the action of a specific catalyst.

[0072] The system of the present invention is conducive to achieving lower cost and more efficient stable separation of products.

[0073] The entire system of the present invention can be designed as an easily portable integrated device, and can also be designed as an integrated sulfur and carbon removal system to achieve low-cost and environmentally friendly treatment of sulfur- and carbon-containing waste gas.

[0074] The present invention is mainly aimed at low-carbon utilization of fossil energy, but it can also be used in the field of air pollution control. Its essence is to fully recover the chemical energy released by SO2 oxidation to reduce the energy consumption of carbon dioxide electrochemical reduction. The relevant strategy can be extended to other small molecule oxidation-coupled carbon reduction systems, which will have a wide impact in the field of energy-related research.

Claims

1. A sulfur-carbon integrated removal system, characterized in that: include: An electrolysis system (1), a renewable energy power generation device (2), a UPS rectifier (3), a power supply (4), a first valve (5), a cathode liquid storage tank (6), a first liquid pump (7), a second liquid pump (8), a second valve (9), an anode reaction zone (10), a cathode reaction zone (11), a third liquid pump (12), a third valve (13), a gas-liquid separator (14), a liquid product collecting device (15), a gas dryer (16), a gas product collecting device (17), an extraction device (18), an H2SO4 collecting device (19), a fourth valve (20), a fifth valve (21), an anode liquid storage tank (22), a fourth liquid pump (23) and a reduction tower (24); The electric energy of the power source (4) can be provided by the renewable energy power generation device (2) after being processed by the UPS rectifier (3); The electrolysis system (1) is connected to a power supply (4) for power supply via a wire; an anode reaction zone (10) is provided on one side of the electrolysis system (1), and a cathode reaction zone (11) is provided on the other side; the anode reaction zone (10) and the cathode reaction zone (11) are separated by a proton exchange membrane; the cathode reaction zone (11) of the electrolysis system (1) is connected to the liquid inlet of the cathode liquid storage tank (6) via a liquid infusion tube through a first valve (5), the bottom end of the cathode liquid storage tank (6) is connected to the first liquid pump (7) via a liquid infusion tube, and the liquid outlet of the first liquid pump (7) is connected to the cathode reaction zone (11) of the electrolysis system (1) via a liquid infusion tube; The cathode liquid storage tank (6) is connected to the third liquid pump (12) through a liquid infusion tube, and the liquid outlet of the third liquid pump (12) is connected to the gas-liquid separator (14) through a liquid infusion tube; the side end of the gas-liquid separator (14) is connected to the cathode liquid storage tank (6) through a liquid infusion tube via a third valve (13); the lower end of the gas-liquid separator (14) is connected to the liquid product collecting device (15) through a liquid infusion tube; the top end of the gas-liquid separator (14) is connected to the gas dryer (16) through a gas delivery tube, and the outlet of the gas dryer (16) is connected to the gas product collecting device (17) through the gas delivery tube; The anode reaction zone (10) of the electrolysis system (1) is connected to the liquid inlet of the anode liquid storage tank (22) through a liquid infusion tube via a second valve (9), the bottom end of the anode liquid storage tank (22) is connected to the second liquid pump (8) through a liquid infusion tube, and the liquid outlet of the second liquid pump (8) is connected to the anode reaction zone (10) of the electrolysis system (1) through a liquid infusion tube; The anode liquid storage tank (22) is connected to the fourth liquid pump (23) via a liquid infusion tube, the liquid outlet of the fourth liquid pump (23) is connected to the reduction tower (24) via a liquid infusion tube, and the lower end of the reduction tower (24) is connected to the anode liquid storage tank (22) via a liquid infusion tube through a fourth valve (20); The anode liquid storage tank (22) is connected to the extraction device (18) via a liquid infusion tube via a fifth valve (21), and a side liquid outlet of the extraction device (18) is connected to the anode liquid storage tank (22) via a liquid infusion tube.

2. The sulfur-carbon integrated removal system according to claim 1, characterized in that: The liquid outlet at the bottom of the extraction device is connected to the H2SO4 collecting device (19) through a liquid infusion tube.

3. The sulfur-carbon integrated removal system according to claim 1, characterized in that: The cathode reaction zone (11) is filled with a NaHCO3 solution.

4. The sulfur-carbon integrated removal system according to claim 1, characterized in that: A solution containing an organic electrical coupling agent Q is arranged inside the anode reaction zone (10). The types of the organic electrical coupling agent Q include AQDS, ADS, BQDS, Fe(CN)63- / 4-, MDEA, Tiron, TironA and its derivatives, phenol and its derivatives, phenothiazine derivatives and ferrocene derivatives or organic matter with PCET electrochemical reaction activity.

5. The sulfur-carbon integrated removal system according to claim 1, characterized in that: The reduction tower (24) is provided with a catalyst capable of catalyzing the reaction between SO2 and an organic electric coupling agent, including a platinum catalyst, a palladium catalyst, V / Al2O3, graphite, activated carbon, a gold catalyst, RuO2, WO3 and a substance capable of catalyzing the oxidation reaction of SO2.

6. The sulfur-carbon integrated removal system according to claim 5, characterized in that: The cathode reaction zone (11) is provided with a catalyst capable of catalyzing a CO2 reduction reaction, including Ag, Fe, Cu-based catalysts, cobalt phthalocyanine, nickel phthalocyanine and a catalyst capable of catalyzing a CO2RR reaction.

7. A sulfur-carbon integrated removal method, characterized in that: The steps include: S1, constructing the sulfur-carbon integrated removal system as described in claims 1 to 6; S2, the organic electric coupling agent QH2 undergoes oxidation reaction in the anode reaction zone (10) of the electrolysis system (1) to Q and releases protons H + The solution passes through the second valve (9) and enters the reduction tower (24) under the action of the fourth pumping pump (23) to react with SO2 to generate QH2 and sulfuric acid. The QH2 returns to the anode reaction zone (10) under the action of the second pumping pump (8) to complete the cycle. The solution in the anode storage tank passes through the extraction device (18) and is collected in the H2SO4 collection device (19). The protons generated by the anode reaction pass through the proton exchange membrane to reach the cathode reaction zone (11) and react with CO2 under the action of the catalyst to generate a CO2 reduction reaction. The solution after the reaction passes through the first valve (5) and reaches the gas-liquid separator (14) under the action of the third pumping pump (12). The gas product passes through the gas drying tube (16) and enters the gas product collection device (17). The liquid product enters the liquid product collection device (15). The self-reduction semi-decoupled sulfur-carbon integrated removal system constructed by the above steps can achieve sulfur-carbon integrated removal. The overall reaction formula of the entire system is: CO2+4SO4+6H20=CH4+4H2SO4.

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