A method and system for the synergistic and comprehensive resource utilization treatment of mixed H2S and CO2 waste gas

Abstract

This invention discloses a method and system for the synergistic and comprehensive resource-based treatment of mixed H₂S and CO₂ waste gas, belonging to the field of resource recycling technology. It adopts a closed-loop process: "staged pretreatment—selective enrichment of H₂S—CO₂ dual-tower temperature-switching adsorption and capture—non-thermal plasma synergistic catalytic directional conversion—syngas merging and upgrading—gas turbine power generation—waste heat closed-loop recovery." Through stepwise enrichment, it achieves high-concentration of low-concentration H₂S and CO₂; through non-thermal plasma synergistic catalysis, it achieves directional conversion of sulfur and carbon at low temperature and normal pressure; and through syngas merging and waste heat recovery, it achieves a dual closed loop of materials and energy. H₂S removal rate ≥99.9%, CO₂ capture and utilization rate ≥92%, sulfur product purity ≥99.5%, carbon emission reduction rate ≥90%, and dry operation with no secondary pollution. It solves the core defects of existing technologies such as fragmented treatment, poor adaptability to operating conditions, low resource utilization, and high energy consumption. It can be widely used in the synergistic treatment and low-carbon resource utilization of sulfur- and carbon-containing waste gases in industries such as oil and gas fields, coal-based activated carbon production, and coal chemical industry.

Description

Technical Field

[0001] This invention belongs to the fields of energy conservation and environmental protection, carbon capture, utilization and storage (CCUS), sulfur resource recovery and distributed energy technology. Specifically, it relates to a method and system for the synergistic and full-resource treatment of H2S and CO2 that can be adapted to both associated gas from oil fields and tail gas from coal-based activated carbon production. Background Technology

[0002] Under the national policy of high-quality development for ecological protection in the Yellow River Basin, the treatment and resource utilization of sulfur- and carbon-containing waste gases from industries such as oil and gas field development and coal-based activated carbon production have become rigid demands. Associated gas from major domestic oil and gas fields such as Shengli Oilfield generally contains 0.1–0.5 vol% H2S and 5–15 vol% CO2, which are typical low-concentration sulfur- and carbon-containing associated gas. my country is the world's largest producer of coal-based activated carbon, accounting for over 90% of global production capacity. The carbonization and activation processes of activated carbon generate large amounts of high-temperature exhaust gas containing H2S, CO2, CO, H2, and tar, characterized by complex composition, large fluctuations, and the coexistence of toxic, harmful, and combustible components.

[0003] Existing technologies for treating these two types of gas sources have the following core, specific, and unavoidable shortcomings:

[0004] (1) Extremely poor scenario adaptability and no universal process: Existing desulfurization and decarbonization processes are all designed for a single gas source. The alkanolamine method and the Claus method are only suitable for high-concentration acid gas in coal chemical industry. They cannot handle the low-concentration H2S / CO2 and high hydrocarbon conditions of associated gas in oil fields, nor can they adapt to the high tar and wide fluctuation characteristics of activated carbon tail gas. There is no technology that can simultaneously achieve the coordinated treatment of two types of gas sources. Enterprises need to build two separate treatment systems, which increases investment costs by more than 120%.

[0005] (2) Fragmented treatment, unable to achieve full resource utilization: Existing technologies are mostly for the treatment of single pollutants. Desulfurization processes only remove H2S, and decarbonization processes only capture CO2. The two are independent of each other and cannot achieve synergistic resource utilization of sulfur and carbon. The CO and H2 combustible components in activated carbon tail gas are mostly treated by direct combustion and venting, which not only causes serious energy waste, but also produces SO2 and NO. x Secondary pollution; there is currently no technology that can simultaneously achieve a closed-loop process of "desulfurization and decarbonization - sulfur recovery - carbon conversion - energy recovery".

[0006] (3) The mainstream treatment technologies cause serious secondary pollution and pose extremely high environmental risks: More than 90% of enterprises use the traditional process of "electrostatic tar removal + direct combustion + alkaline desulfurization" to treat the tail gas of coal-based activated carbon production. The CO and H2 in the tail gas are directly burned and discharged into the air, which not only wastes a lot of high-quality combustible energy, but also generates SO2 due to the combustion of H2S. Therefore, an alkaline desulfurization device is required, which generates 1,200 tons of high-salt desulfurization waste liquid per 10,000 tons of production capacity per year. The hazardous waste disposal cost is as high as RMB 1.8 million per year, and the environmental compliance risk is extremely high. A few enterprises use wet desulfurization and decarbonization processes, which also have the problems of large waste liquid generation, serious equipment corrosion, and high operating costs.

[0007] (4) The operating conditions of activated carbon production are severely out of sync with the industry, resulting in extremely poor adaptability: The operating conditions of activated carbon furnaces fluctuate greatly. During start-up, shutdown, and adjustment of activators, the flow rate and composition of exhaust gas can fluctuate by ±30%, and the tar content can fluctuate by 500-2000 mg / Nm³. Existing treatment technologies cannot adapt to the wide range of operating condition fluctuations, and are prone to problems such as tar clogging of pipelines, poisoning and deactivation of adsorbents / catalysts, and substandard treatment. They cannot achieve long-term stable operation, and the average annual operating time of treatment devices in the industry is less than 4000 hours, which is far below the design requirements.

[0008] (5) High safety risks and low automation: CO and H2 in activated carbon tail gas are flammable and explosive gases, and H2S is a highly toxic gas. Most of the existing treatment devices are manually operated and lack a complete safety interlock system. The safety risks of toxic gas leakage and combustible gas explosion are extremely high, and related safety accidents have occurred many times in the industry.

[0009] (6) High energy consumption and no closed-loop energy design: Existing desulfurization and decarbonization processes require a large amount of steam and electricity, resulting in extremely high operating costs; the Claus process requires high-temperature reaction conditions above 200°C, resulting in high energy consumption and safety risks; existing technologies do not couple the treatment process with energy recovery, making it impossible to achieve self-sufficiency in electricity for the plant area, and the electricity consumption cost of activated carbon production enterprises accounts for more than 30% of the total cost, further increasing the burden on enterprises.

[0010] (7) Low catalytic conversion efficiency and poor adaptability to operating conditions: The existing H2S-CO2 catalytic conversion technology, represented by the Shanxi Coal Chemistry Institute of the Chinese Academy of Sciences, uses Al2O3 supported metal sulfide catalysts. It is only suitable for one-step conversion of high-concentration mixed acid gas. It has poor adaptability to the low-fluctuation, high-purity gas source after stepwise enrichment involved in this invention. The CO2 conversion rate is generally less than 20% at normal pressure and low temperature. Moreover, the catalyst is easily poisoned and deactivated by tar and heavy hydrocarbons, and cannot operate stably for a long period of time.

[0011] (8) Severe secondary pollution and high environmental risks: Existing wet desulfurization and decarbonization processes generate a large amount of high-salt organic wastewater, with a wastewater generation of ≥0.002 m³ per ton of gas treated.3 Hazardous waste disposal costs are extremely high; the tail gas from the Claus process still requires secondary hydrogenation treatment, making it impossible to achieve emission standards and posing significant environmental risks.

[0012] Therefore, developing a universal, fully resource-efficient, zero-pollution, and energy-closed-loop process for treating sulfur- and carbon-containing waste gases across two scenarios has become an urgent need for the industry and is of great significance to achieving the national dual-carbon goals. Summary of the Invention

[0013] The purpose of this invention is to provide a method and system for the synergistic and comprehensive resource utilization treatment of H2S and CO2 mixed waste gas, aiming to overcome the following technical problems: (1) solving the problem that existing technologies cannot simultaneously adapt to the dual scenarios of associated gas from oil fields and tail gas from activated carbon plants, resulting in fragmented treatment and high investment costs; (2) solving the problem that existing technologies cannot achieve synergistic and comprehensive resource utilization of sulfur and carbon, resulting in the disconnect between pollutant treatment and energy recovery; (3) solving the problem that existing processes have high energy consumption, lack energy closed-loop design, and have high operating costs; (4) solving the problem that existing catalytic technologies have poor low-temperature activity, are prone to poisoning and deactivation, and cannot adapt to the wide range of operating conditions in industrial sites; (5) solving the problem that existing wet processes cause serious secondary pollution and high environmental risks.

[0014] To achieve the above objectives, the first aspect of the present invention provides a method for the synergistic and comprehensive resource utilization treatment of mixed H2S and CO2 waste gas, comprising the following steps:

[0015] S1 Raw Material Grading Pretreatment: Pretreatment is performed on the mixed H2S and CO2 waste gas, which is at least one of the following: associated gas from oil fields and tail gas from activated carbon plants. Impurities in the mixed gas are removed, while H2S and CO2 are retained. The associated gas from oil fields includes CH4 70–80 vol%, C2–C5 10–15 vol%, H2S 0.1–0.5 vol%, CO2 5–15 vol%, and N2 balance. The tail gas from activated carbon plants includes CO 15–30 vol%, H2 10–20 vol%, CO2 8–15 vol%, H2S 0.1–0.5 vol%, and tar 500–2000 mg / Nm³. 3 The nitrogen balance is maintained at a temperature of 80–150°C.

[0016] Selective adsorption and high concentration enrichment of H2S: H2S in the pretreated gas is adsorbed by a topological polymer adsorbent. After adsorption, the gas is desorbed by steam hydrolysis. The desorbed gas is then condensed and dehydrated to obtain high-concentration H2S gas with a purity ≥95%.

[0017] S3 CO2 Dual-Tower Adsorption Capture and Purification: Coal-based activated carbon is then used to adsorb CO2 from the pretreated gas. After adsorption, vacuum heating regeneration is performed to obtain high-concentration CO2 gas with a purity ≥96%. After the pretreated gas passes through steps S2 and S3 to adsorb H2S and CO2 in sequence, the remaining gas is the purified tail gas.

[0018] S4 Non-thermal plasma synergistic catalytic directional conversion: The high-concentration H2S and CO2 mixture obtained from the regeneration in steps S2 and S3 is transported to the reactor. The reactor is equipped with a catalyst, and under the action of the catalyst, H2S and CO2 react to generate syngas and sulfur.

[0019] S5 delivers catalytic synthesis gas, or a mixture of catalytic synthesis gas and at least one of purified tail gas and activated carbon plant pretreatment gas, to the gas turbine for power generation to supplement the plant's electricity consumption.

[0020] S6 waste heat closed-loop recovery: recovers the heat from the high-temperature flue gas discharged from the gas turbine and sends it to the shell-and-tube waste heat boiler to produce saturated steam.

[0021] Specifically, the associated gas pretreatment process in the oilfield is as follows: the associated gas from the oilfield undergoes sequential processing including cyclone dust removal, 1μm precision filtration, dehydration, and heavy hydrocarbon removal to obtain pretreated associated gas with a dust concentration ≤1mg / Nm³. 3 The water dew point is ≤-10℃, and the heavy hydrocarbon content is ≤0.5 vol%. The pretreatment process for activated carbon production tail gas is as follows: the activated carbon production tail gas successively undergoes indirect cooling, cyclone dust removal, high-voltage electrostatic precipitator for tar, 1μm precision filtration, and dehydration treatment to obtain pretreated gas for the activated carbon plant. The gas temperature is ≤40℃, and the dust concentration is ≤1 mg / Nm³. 3 Water dew point ≤ -10℃, tar content ≤ 10mg / Nm 3 Tar removal rate ≥99%.

[0022] In step S2 of this invention, the adsorption and desorption of H2S are completed in a dual-tower adsorption system of topological polymer adsorbent, using an alternating operation mode of one tower in use and one in standby. H2S is selectively adsorbed at room temperature and pressure. After adsorption saturation, desorption is performed using saturated steam at 110–120℃ and 0.2 MPa. The desorbed gas is condensed and dehydrated to obtain high-concentration H2S gas with a purity ≥95%, and the total H2S removal rate ≥99.9%. The topological polymer adsorbent is an aluminosilicate-based hyperbranched topological polymer modified with diethylenetriamine, with a hyperbranching degree ≥80%, a static adsorption capacity for H2S ≥2.3 mmol / g, an adsorption selectivity of H2S / CH4 ≥200:1, an adsorption selectivity of H2S / N2 ≥180:1, and an anti-tar poisoning ability ≥1000 mg / Nm³. 3In step S3 of this invention, the adsorption and desorption of CO2 are completed in a coal-based activated carbon dual-tower temperature-variable adsorption system, employing an alternating operation mode of one tower in use and one in standby. CO2 is selectively adsorbed at 35–45℃ and normal pressure. After adsorption saturation, regeneration is achieved through vacuum heating at 110–130℃ and a vacuum degree ≤100Pa. The regenerated gas is then condensed and purified to obtain high-concentration CO2 gas with a purity ≥96%, a CO2 capture efficiency ≥92%, and a CO2 residue in the purified gas ≤0.5 vol%. The coal-based activated carbon adsorbent is prepared from Zhundong long-flame coal using a potassium carbonate cyclic activation method, with a specific surface area ≥1100 m² / g and a pore volume ≥0.5 cm³. 3 / g, mechanical strength ≥94%, dynamic adsorption capacity for CO2 ≥2.6mmol / g, adsorption selectivity for CO2 / CH4 ≥35:1.

[0023] The high-concentration H2S and CO2 mixture obtained from step S3 is precisely mixed in a molar ratio of 2:1, preheated to 120°C in a preheater, and then enters a coaxial dielectric barrier discharge nonthermal plasma catalytic reactor. The reactor is filled with a supported catalyst capable of catalyzing the directional conversion of H2S and CO2 into sulfur, CO, and H2. The reaction is carried out at atmospheric pressure, 120–180°C, and a reaction space velocity of 600–1000 h⁻¹. -1 Under conditions of discharge voltage of 10-20kV, discharge frequency of 5-20kHz, and power density of 200-400W / L, a directional conversion reaction occurs. The reaction products are separated by two-stage condensation to obtain industrial sulfur with a purity of ≥99.5%. The gaseous product is catalytic synthesis gas with CO and H2 as the main components.

[0024] Preferably, the supported catalyst in step S4 is a coal-based activated carbon supported composite catalyst, using Zhundong coal-based porous activated carbon prepared by potassium carbonate cyclic activation method as the support, and MgS, CaS, Ni3S2, Ni3S2-MgS or ZnS-MoS2 as active precursors. The specific preparation method is as follows: the support is treated with dilute nitric acid reflux to introduce oxygen-containing functional groups on the surface, washed and dried, and then placed in the metal salt solution of the corresponding active precursor for ultrasonic impregnation at room temperature. After static aging, it is filtered and dried to obtain metal oxide precursors MgO, CaO, NiO, NiO-MgO or ZnO-MoO3. The loading of the metal oxide precursor in the support is 5-30%. Then, H2S / N2 mixed gas is introduced into the precursor, and in-situ sulfidation activation is carried out at atmospheric pressure and 100-150℃ for 2-4 hours to obtain the catalyst.

[0025] A second aspect of this invention provides a synergistic, all-resource-based treatment system for mixed H2S and CO2 waste gas, comprising a raw material pretreatment unit, an H2S enrichment unit, a CO2 dual-tower capture unit, and a non-thermal plasma catalytic unit. The raw material pretreatment unit is used to remove dust, water, condensate oil, and heavy hydrocarbons from associated gas from oil fields, reducing the dust concentration in the associated gas to ≤1 mg / Nm³. 3 Water dew point ≤ -10℃, heavy hydrocarbon content ≤ 0.5 vol%; or used to remove dust, water, and tar from the tail gas of coal-based activated carbon production, so that the tail gas temperature is ≤ 40℃ and the dust concentration is ≤ 1 mg / Nm³. 3 Water dew point ≤ -10℃, tar content ≤ 10mg / Nm 3 The raw material pretreatment unit is sequentially connected to the H2S enrichment unit and the CO2 dual-tower capture unit. The H2S enrichment unit is used to adsorb and regenerate H2S in the H2S and CO2 mixed waste gas, and the CO2 dual-tower capture unit is used to absorb and regenerate CO2 in the H2S and CO2 mixed gas. The regeneration gas outlets of the H2S enrichment unit and the CO2 dual-tower capture unit are both connected to the non-thermal plasma catalytic unit, which sends the regenerated H2S and CO2 into the non-thermal plasma catalytic unit. Under the action of the catalyst, the non-thermal plasma catalytic unit converts H2S and CO2 into sulfur, CO and H2 in a directed manner.

[0026] In one implementation, the raw material pretreatment unit includes an associated gas pretreatment unit for oil fields and a tail gas pretreatment unit for coal-based activated carbon production. The associated gas pretreatment unit for oil fields includes a first gas-liquid separator, a first cyclone separator, a first 1μm coalescing precision filter, a first molecular sieve dehydration tower, a condenser, and a second gas-liquid separator connected in sequence. The tail gas pretreatment unit for coal-based activated carbon production includes a gas cooler, a second cyclone separator, a high-voltage electrostatic precipitator for tar, a second 1μm precision filter, and a second molecular sieve dehydration tower connected in sequence.

[0027] In one implementation, the H2S enrichment unit includes two parallel topological polymer adsorption towers, a steam generator, a desorption tower, and a condenser-liquid separator. Each of the two topological polymer adsorption towers is equipped with a pretreated gas inlet, a desulfurization gas outlet, a steam inlet, and an H2S outlet. The two topological polymer adsorption towers adsorb alternately, and are regenerated after adsorption. During adsorption, the pretreated gas inlet and desulfurization gas outlet of the corresponding topological polymer adsorption tower are open, while the steam inlet and H2S outlet are closed. The pretreated gas inlet is connected to an associated gas pretreatment unit in an oilfield or a tail gas pretreatment unit in coal-based activated carbon production, and the desulfurization gas outlet is connected to a CO2... The dual-tower collection unit is interconnected. During regeneration, the pretreatment gas inlet and desulfurization gas outlet of the corresponding topological polymer adsorption tower are closed, while the steam inlet and H2S outlet are opened. The steam inlet is connected to the steam generator, and the H2S outlet is sequentially connected to the desorption tower, the condenser gas-liquid separator, and the non-thermal plasma catalytic unit. The CO2 dual-tower collection unit includes two coal-based activated carbon adsorption towers, a Roots-rotary vane vacuum regeneration unit, and a condensation and purification device arranged in parallel. Each of the two coal-based activated carbon adsorption towers is equipped with a desulfurization gas inlet, a purified tail gas outlet, and a CO2 outlet. Two coal-based activated carbon adsorption towers alternately adsorb the gas. After adsorption, regeneration is performed. During adsorption, the desulfurization gas inlet and the purified tail gas outlet of the corresponding coal-based activated carbon adsorption tower are opened, and the CO2 outlet is closed. The desulfurization gas inlet and the desulfurization gas outlet are connected, and the purified tail gas is discharged from the purified tail gas outlet. During regeneration, the desulfurization gas inlet and the purified tail gas outlet of the corresponding coal-based activated carbon adsorption tower are closed, and the CO2 outlet is opened. The CO2 outlet is connected in sequence to the Roots-rotary vane vacuum regeneration unit, the condensation purification device, and the non-thermal plasma catalytic unit.

[0028] In one implementation, the non-thermal plasma catalytic unit includes a static mixer, a preheater, a coaxial dielectric barrier discharge plasma catalytic reactor, a sulfur condenser and a sulfur flake generator connected in sequence. The coaxial dielectric barrier discharge plasma catalytic reactor is filled with a supported catalyst capable of catalyzing the directional conversion of H2S and CO2 into sulfur, CO and H2.

[0029] In one implementation, the coaxial dielectric barrier discharge plasma catalytic reactor is a horizontal structure, comprising a stainless steel inner high-voltage electrode, a first high-purity quartz dielectric tube, a catalyst-packed bed, a second high-purity quartz dielectric tube, a stainless steel external grounding electrode, an aluminum silicate insulation layer, a porous gas distributor, and a flange sealing end cap. The stainless steel inner high-voltage electrode, the first high-purity quartz dielectric tube, the catalyst-packed bed, the second high-purity quartz dielectric tube, the stainless steel external grounding electrode, and the aluminum silicate insulation layer are arranged concentrically from the inside out, forming a tubular structure. A porous gas distributor is installed at each end of the tubular structure, which is then sealed by the flange sealing end cap. An inlet and an outlet are respectively provided on the flange sealing end cap. The inlet, the inlet-end porous gas distributor, the catalyst-packed bed, the outlet-end porous gas distributor, and the outlet are sequentially connected. The coaxial dielectric barrier discharge plasma catalytic reactor is filled with a supported catalyst.

[0030] Furthermore, the H2S and CO2 mixed waste gas synergistic resource recovery treatment system also includes a gas turbine power generation unit and a waste heat recovery unit. The gas turbine power generation unit is used to generate electricity from the catalytic synthesis gas and / or activated carbon purified tail gas, and the waste heat recovery unit is used to recover the high-temperature flue gas generated by the gas turbine and convert it into steam.

[0031] Furthermore, the H2S and CO2 mixed gas synergistic resource utilization treatment system also includes a DCS intelligent control unit, comprising an H2S leakage interlock module, an over-temperature and over-pressure interlock module, a combustible gas leakage interlock module, a tar exceeding standard interlock module, an adsorption tower switching interlock module, a gas turbine fault interlock module, and an emergency shutdown interlock module; H2S The leakage interlock module is used to monitor the H2S concentration in equipment and pipelines in real time and promptly detect H2S leaks. The over-temperature and over-pressure interlock module is used to monitor the operating temperature and pressure of equipment in real time and promptly detect equipment operating at over-temperature or over-pressure. The combustible gas leakage interlock module is used to monitor the content of combustible gases such as CH4, CO, and H2 in equipment and pipelines in real time and promptly detect combustible gas leaks. The tar exceeding standard interlock module is installed at the outlet of the high-voltage electrostatic precipitator to monitor tar content in real time and promptly detect tar exceeding the standard at the outlet. The adsorption tower switching interlock module is used to switch between two topological polymer adsorption towers and two coal-based activated carbon adsorption towers. Based on the control of the corresponding programmable pneumatic shut-off valves, it realizes the switching of adsorption and regeneration processes, with a switching time ≤10s and no pressure fluctuations. The gas turbine fault interlock module is used to promptly detect gas turbine faults. (H2S) The leakage interlock module, over-temperature and over-pressure interlock module, combustible gas leakage interlock module, tar exceeding standard interlock module, and gas turbine fault interlock module are all connected to the emergency shutdown interlock module to perform emergency shutdown control based on the detection situation.

[0032] The DCS intelligent control unit is electrically connected to all transmitters, valves, pumps, heaters, plasma power supplies, and generator sets within the system, enabling fully automated control, real-time data acquisition, safety interlock protection, and remote monitoring.

[0033] The plasma power supply of the non-thermal plasma catalytic reactor is interlocked with the DCS intelligent control unit, which can automatically adjust the discharge voltage and frequency according to the feed gas flow rate and composition. The adjustment range is: voltage 10-20kV, frequency 5-20kHz.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] (1) For the first time, dual-scenario universal treatment is achieved: one process can be adapted to two typical sulfur- and carbon-containing gas sources, namely associated gas from oil fields and tail gas from activated carbon plants. There is no need to build two separate systems, reducing investment costs by more than 55% and reducing the land area by 40%, filling a gap in the industry.

[0036] (2) Complete resource utilization and zero emissions, with maximum environmental benefits: H2S is converted into high-purity industrial sulfur, CO2 is converted into syngas, and combustible components are used for power generation, achieving 100% resource utilization of pollutants and no discharge of waste gas, wastewater, and solid waste; H2S removal rate ≥99.9%, far below the national emission standard limit, with an annual carbon emission reduction of up to 22,000 tons / 10,000 Nm³. 3 The processing capacity of / h fully complies with the requirements of the dual-carbon strategy.

[0037] (3) Closed-loop energy self-sufficiency, revolutionary improvement in economic benefits: The system achieves self-heating and self-powering, reducing operating costs by more than 40% compared to traditional processes; it simultaneously produces sulfur products and clean electricity, with annual revenue reaching 8 million yuan / 10,000 Nm³. 3 With a processing capacity of / h and an investment payback period of ≤3 years, it has completely changed the industry status quo of environmental governance that is "only input and no output".

[0038] (4) Significantly improved catalytic performance and stability: The synergistic effect of non-thermal plasma and self-developed catalyst results in H2S conversion rate ≥99% and CO2 conversion rate ≥36% at 150℃ and normal pressure, which is more than 15 percentage points higher than the existing technology; the catalyst has an activity retention rate of ≥92% after 1000h continuous operation, which solves the industry pain point of easy poisoning and deactivation.

[0039] (5) Extremely strong industrial adaptability and safety: The whole process operates at low temperature and normal pressure, without high temperature and high pressure equipment, and the safety risk is extremely low; the process load adjustment range is 30% to 110%, which can adapt to the fluctuation of gas source flow and composition ±30%; the whole process is controlled by DCS automatic control and multiple safety interlocks, which can realize unattended continuous operation, with an annual operating time of ≥7200h, perfectly adapting to industrial site conditions.

[0040] (6) Low transformation cost and high promotion value: This process can directly upgrade the tail gas treatment device of existing activated carbon enterprises. The transformation cost is only 40% of that of new equipment, and the transformation cycle is ≤3 months. It can be quickly promoted to activated carbon production enterprises across the country, which is of great significance to the green and low-carbon transformation of the entire industry. Attached Figure Description

[0041] Figure 1 is a schematic diagram of the structure of the H2S and CO2 mixed waste gas synergistic full resource utilization treatment system involved in this invention.

[0042] Figure 2 is a schematic diagram of the raw material pretreatment unit, H2S enrichment unit, CO2 dual-tower capture unit and non-thermal plasma catalysis unit involved in this invention.

[0043] Figure 3 is a schematic diagram of the coaxial dielectric barrier discharge nonthermal plasma catalytic reactor involved in this invention. Detailed Implementation

[0044] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0045] A method for the synergistic and comprehensive resource recovery treatment of mixed H2S and CO2 waste gas includes the following steps:

[0046] S1 Raw Material Grading Pretreatment: Pretreatment of mixed H2S and CO2 waste gas, which is at least one of associated gas from oil fields and tail gas from activated carbon plants, to remove impurities from the mixed gas while retaining H2S and CO2.

[0047] In step S1 of this invention, associated gas from oil fields refers to typical low-concentration associated gas containing sulfur and carbon generated during oil exploration. Its composition includes CH4 70-80 vol%, C2-C5 10-15 vol%, H2S 0.1-0.5 vol%, CO2 5-15 vol%, and N2 balance.

[0048] In step S1 of this invention, the activated carbon plant tail gas refers to the large amount of high-temperature tail gas containing H2S, CO2, CO, H2, and tar generated during the carbonization and activation stages of coal-based activated carbon production. It includes: CO 15-30 vol%, H2 10-20 vol%, CO2 8-15 vol%, H2S 0.1-0.5 vol%, and tar 500-2000 mg / Nm³. 3The nitrogen balance is maintained at a temperature of 80–150°C.

[0049] The pretreatment process for associated gas from oilfields is as follows: the associated gas undergoes sequential processing including cyclone dust removal, 1μm precision filtration, dehydration, and heavy hydrocarbon removal to obtain pretreated associated gas with a dust concentration ≤1mg / Nm³. 3 The water dew point is ≤-10℃ and the heavy hydrocarbon content is ≤0.5 vol%. As a preferred embodiment, 3A molecular sieves are used for deep dehydration.

[0050] The pretreatment process for activated carbon production exhaust gas is as follows: the exhaust gas sequentially undergoes indirect cooling (cooling to below 60℃), cyclone dust removal, high-voltage electrostatic precipitator for tar, 1μm precision filtration, and dehydration to obtain pretreated gas for the activated carbon plant. This gas has a temperature ≤40℃ and a dust concentration ≤1mg / Nm³. 3 Water dew point ≤ -10℃, tar content ≤ 10mg / Nm 3 The tar removal rate is ≥99%. As a preferred embodiment, 4A molecular sieves are used for deep dehydration. The high-voltage electrostatic precipitator voltage is 30-35kV.

[0051] Step S1 addresses the characteristics of associated gas from oil fields being high in hydrocarbons and activated carbon tail gas being high in tar by designing differentiated pretreatment pathways to thoroughly remove catalyst poisons, avoid poisoning and deactivation of adsorbents and catalysts, and achieve a single process adaptable to two gas sources.

[0052] Selective adsorption and high concentration enrichment of H2S: H2S in the pretreated gas is adsorbed by a topological polymer adsorbent. After adsorption, the gas is desorbed by steam hydrolysis. The desorbed gas is then condensed and dehydrated to obtain high-concentration H2S gas with a purity ≥95%.

[0053] In step S2 of this invention, the adsorption and desorption of H2S are completed in a dual-tower adsorption system of topological polymer adsorbent, using an alternating operation mode of one in use and one in standby. H2S is selectively adsorbed at room temperature and pressure. After adsorption saturation, H2S is desorbed by hydrolysis with saturated steam at 110-120℃ and 0.2MPa. The desorbed gas is condensed and dehydrated to obtain high-concentration H2S gas with a purity ≥95%. The total H2S removal rate is ≥99.9%, and the regeneration efficiency of the adsorbent after 100 cycles is ≥98%.

[0054] In step S2 of this invention, the topological polymer adsorbent is prepared by modifying an aluminosilicate-based hyperbranched topological polymer with diethylenetriamine. The degree of hyperbranching is ≥80%, the static adsorption capacity for H2S is ≥2.3 mmol / g, the adsorption selectivity for H2S / CH4 is ≥200:1, the adsorption selectivity for H2S / N2 is ≥180:1, and the resistance to tar poisoning is ≥1000 mg / Nm³. 3 .

[0055] As one approach, the specific preparation method of topological polymer adsorbents is as follows:

[0056] (1) Take one of tetraethyl orthosilicate, silica sol or water glass as the silicon source, and take one of aluminum isopropoxide, aluminum nitrate, aluminum chloride or sodium aluminate as the aluminum source. Add ethanol and deionized water and mix. Adjust the pH of the system to 2–4 and carry out hydrolysis reaction for 1–4 h to obtain aluminum-silicon precursor sol.

[0057] (2) Add an epoxy-containing silane coupling agent to the aluminum-silicon precursor sol, wherein the epoxy-containing silane coupling agent is γ-glycidyl etheroxypropyltrimethoxysilane or γ-glycidyl etheroxypropyltriethoxysilane, and continue stirring for 2–6 h to allow it to undergo a condensation reaction with the aluminum-silicon precursor to form an epoxy-containing aluminum-silicon-based hyperbranched precursor;

[0058] (3) The above-mentioned epoxy-containing aluminum-silicon-based hyperbranched precursors were aged at 60–100 °C for 6–24 h, and after washing, filtration and drying, epoxy-modified aluminum-silicon-based hyperbranched topological polymers were obtained.

[0059] (4) The epoxy-modified aluminum-silicon-based hyperbranched topological polymer is dispersed in anhydrous ethanol, methanol or toluene, and diethylenetriamine is added. The mixture is refluxed at 60–90 °C for 6–24 h to allow the amino groups in the diethylenetriamine to undergo a ring-opening grafting reaction with the epoxy groups.

[0060] (5) After the reaction is complete, the obtained solid product is washed with ethanol and deionized water until neutral, and then dried under vacuum at 60–100 °C for 6–12 h to obtain diethylenetriamine modified aluminum silicon-based hyperbranched topological polymer adsorbent.

[0061] S3 CO2 Dual-Tower Adsorption Capture and Purification: Coal-based activated carbon is then used to adsorb CO2 from the pretreated gas. After adsorption, vacuum heating regeneration is performed to obtain high-concentration CO2 gas with a purity ≥96%. After the pretreated gas passes through steps S2 and S3 to adsorb H2S and CO2 in sequence, the remaining gas is the purified tail gas.

[0062] In step S3 of this invention, the adsorption and desorption of CO2 are completed in a coal-based activated carbon dual-tower temperature-switching adsorption system. The system adopts an alternating operation mode of one in use and one in standby. CO2 is selectively adsorbed at 35-45℃ and normal pressure. After adsorption saturation, the system is regenerated by vacuum heating at 110-130℃ and vacuum degree ≤100Pa. The regenerated gas is purified by condensation to obtain high-concentration CO2 gas with a purity ≥96%, CO2 capture efficiency ≥92%, and CO2 residue in the purified gas ≤0.5 vol.

[0063] In step S3 of this invention, the coal-based activated carbon adsorbent is prepared using Zhundong long-flame coal as raw material via a potassium carbonate cyclic activation method, with a specific surface area ≥1100 m² / g and a pore volume ≥0.5 cm³. 3 / g, mechanical strength ≥94%, dynamic adsorption capacity for CO2 ≥2.6mmol / g, adsorption selectivity for CO2 / CH4 ≥35:1.

[0064] S4 Non-thermal plasma synergistic catalytic directional conversion: The high-concentration H2S and CO2 mixture obtained from the regeneration in steps S2 and S3 is transported to the reactor. The reactor is equipped with a catalyst. Under the action of the catalyst, H2S and CO2 react to produce syngas and sulfur.

[0065] The high-concentration H2S and CO2 mixture obtained from step S3 is precisely mixed in a molar ratio of 2:1, preheated to 120°C in a preheater, and then enters a coaxial dielectric barrier discharge nonthermal plasma catalytic reactor. The reactor is filled with a supported catalyst capable of catalyzing the directional conversion of H2S and CO2 into sulfur, CO, and H2. The reaction is carried out at atmospheric pressure, 120–180°C, and a reaction space velocity of 600–1000 h⁻¹. -1 Under conditions of discharge voltage of 10-20kV, discharge frequency of 5-20kHz, and power density of 200-400W / L, a directional conversion reaction occurs. The reaction products are separated by two-stage condensation to obtain industrial sulfur with a purity of ≥99.5%. The gaseous product is catalytic synthesis gas with CO and H2 as the main components.

[0066] Preferably, the supported catalyst in step S4 is a coal-based activated carbon supported composite catalyst, using Zhundong coal-based porous activated carbon prepared by potassium carbonate cyclic activation method as the support, and MgS, CaS, Ni3S2, Ni3S2-MgS or ZnS-MoS2 as active precursors. The specific preparation method is as follows: the support is treated with dilute nitric acid under reflux to introduce oxygen-containing functional groups on its surface. After washing and drying, it is ultrasonically impregnated in a metal salt solution of the corresponding active precursor at room temperature. After static aging, it is filtered and dried to obtain metal oxide precursors MgO, CaO, NiO, NiO-MgO or ZnO-MoO3. The loading of the metal oxide precursor in the support is 5-35%. Then, H2S / N2 mixed gas is introduced into the precursor, and in-situ sulfidation activation is performed at atmospheric pressure and 100-150℃ for 2-4 hours to obtain the catalyst. More preferably, the catalyst active precursor is Ni3S2-MgS, corresponding to the metal oxide precursor NiO-MgO, wherein the NiO loading is 5-20 wt%, the MgO loading is 5-15 wt%, and the molar ratio of nickel to magnesium is 1:(0.5-3).

[0067] Steps S2-S3 employ a dual-tower adsorption process to enrich H2S and CO2 separately, concentrating the low-concentration feed gas to a high-purity reaction gas of over 95%. This solves the problem of low catalytic conversion efficiency from low-concentration gas sources and achieves a precise ratio of H2S to CO2, providing optimal operating conditions for the catalytic reaction. Step S4 utilizes the synergistic effect of coaxial dielectric barrier discharge plasma and a coal-based activated carbon-supported composite catalyst to achieve the directional conversion of H2S and CO2 at low temperature and atmospheric pressure. Compared to the traditional Claus process, the reaction temperature is reduced by more than 200°C, and the activation energy is reduced by 40%. The H2S conversion rate is ≥99%, the CO2 conversion rate is ≥35%, and the sulfur selectivity is ≥95%.

[0068] The catalytic synthesis gas produced in step S4 includes CO 30-40 vol%, H2 45-55 vol%, and H2S ≤ 20 mg / Nm³. 3 H2O ≤ 100ppm, N2 balance, flow rate 1000~2000Nm 3 The gas contains abundant CO and H2. When treating the exhaust gas from an activated carbon plant, the purified exhaust gas in step S3 contains 15-30 vol% CO and 10-20 vol% H2, which can be further utilized, such as for power generation or metal smelting. Therefore, the method for the synergistic and comprehensive resource utilization of mixed H2S and CO2 waste gas further includes:

[0069] S5 delivers catalytic synthesis gas, or a mixture of catalytic synthesis gas and at least one of purified tail gas and activated carbon plant pretreatment gas, to the gas turbine for power generation to supplement the plant's electricity consumption.

[0070] S6 Waste Heat Closed-Loop Recycling: Heat from the high-temperature flue gas discharged from the gas turbine is recovered and fed into a shell-and-tube waste heat boiler to produce saturated steam. All steam is then transported to the adsorption tower regeneration system and raw material preheating system in step S2, forming an energy closed loop. This waste heat recovery and reuse from power generation flue gas enables the system to be self-heating, completely solving the problem of high energy consumption in existing processes.

[0071] like Figure 1 As shown, a synergistic resource-based treatment system for mixed H2S and CO2 waste gas includes a raw material pretreatment unit, an H2S enrichment unit 3, a CO2 dual-tower capture unit 4, and a non-thermal plasma catalytic unit 5. The raw material pretreatment unit removes dust, water, condensate oil, and heavy hydrocarbons from associated gas from oil fields, ensuring that the dust concentration in the associated gas is ≤1 mg / Nm³. 3 Water dew point ≤ -10℃, heavy hydrocarbon content ≤ 0.5 vol%; or used to remove dust, water, and tar from the tail gas of coal-based activated carbon production, so that the tail gas temperature is ≤ 40℃ and the dust concentration is ≤ 1 mg / Nm³. 3 Water dew point ≤ -10℃, tar content ≤ 10mg / Nm3 The raw material pretreatment unit is sequentially connected to the H2S enrichment unit 3 and the CO2 dual-tower collection unit 4. The H2S enrichment unit 3 is used to adsorb and regenerate H2S in the H2S and CO2 mixed waste gas, and the CO2 dual-tower collection unit 4 is used to absorb and regenerate CO2 in the H2S and CO2 mixed gas. The regeneration gas outlets of both the H2S enrichment unit 3 and the CO2 dual-tower collection unit 4 are connected to the non-thermal plasma catalytic unit 5, which sends the regenerated H2S and CO2 into the non-thermal plasma catalytic unit 5. Under the action of a catalyst, the non-thermal plasma catalytic unit 5 converts H2S and CO2 into sulfur, CO, and H2 in a directed manner.

[0072] As one implementation method, such as Figure 2 As shown, the raw material pretreatment unit includes an oilfield associated gas pretreatment unit 1 and a coal-based activated carbon production tail gas pretreatment unit 2. The oilfield associated gas pretreatment unit 1 includes a first gas-liquid separator 101, a first cyclone separator 102, a first 1μm coalescing precision filter 103, a first molecular sieve dehydration tower 104, a condenser 105, and a second gas-liquid separator 106 connected in sequence. First, the associated gas passes through the first gas-liquid separator 101, where condensate oil, free water, and droplets in the oilfield associated gas are condensed. The remaining gas enters the first cyclone separator 102 for dust removal, then enters the first 1μm coalescing precision filter 103 for filtration, then enters the first molecular sieve dehydration tower 104 to remove moisture, and finally enters the condenser 105 to condense heavy hydrocarbons into liquid. The condensate is further separated from the gaseous phase by the second gas-liquid separator 106. Depending on actual needs, the first molecular sieve dehydration tower 104 can be filled with 3A molecular sieves. The coal-based activated carbon production tail gas pretreatment unit 2 includes a gas cooler 201 (such as a cooler or condenser), a second cyclone separator 202, a high-voltage electrostatic precipitator 203, a second 1μm precision filter 204, and a second molecular sieve dehydration tower 205 connected in sequence. The coal-based activated carbon production tail gas is cooled by the gas cooler 201, then enters the second cyclone separator 202 for dust removal, followed by the high-voltage electrostatic precipitator 203 to remove tar, and finally filtered by the second 1μm precision filter 204 before entering the second molecular sieve dehydration tower 205 to remove moisture. Depending on actual needs, the second molecular sieve dehydration tower 205 can be filled with 4A molecular sieves.

[0073] As one implementation method, the high-voltage electrostatic precipitator is a horizontal honeycomb structure with an electric field strength ≥30kV, equipped with an insulating box constant temperature heating system and an automatic tar discharge system, achieving a tar collection efficiency ≥99% and an outlet tar content ≤10mg / Nm³. 3 This avoids subsequent poisoning and deactivation of adsorbents and catalysts.

[0074] In one implementation, the H2S enrichment unit 3 includes two parallel topological polymer adsorption towers 301, a steam generator 302, a desorption tower 303, and a condenser gas-liquid separator 304. Each of the two topological polymer adsorption towers 301 is equipped with a pretreatment gas inlet, a desulfurization gas outlet, a steam inlet, and an H2S outlet. The two topological polymer adsorption towers 301 adsorb alternately, and are regenerated after adsorption. During adsorption, the pretreatment gas inlet and desulfurization gas outlet of the corresponding topological polymer adsorption tower 301 are open, while the steam inlet and H2S outlet are closed. The pretreatment gas inlet is connected to the associated gas pretreatment unit 1 of the oilfield or the tail gas pretreatment unit 2 of coal-based activated carbon production, and the desulfurization gas outlet is connected to the CO2 outlet. The dual-tower collection unit 4 is connected. During regeneration, the pretreatment gas inlet and desulfurization gas outlet of the corresponding topological polymer adsorption tower 301 are closed, while the steam inlet and H2S outlet are opened. The steam inlet is connected to the steam generator 302, and the H2S outlet is connected sequentially to the desorption tower 303, the condenser-liquid separator 304, and the non-thermal plasma catalytic unit 5. The steam generated by the steam generator 302 enters the topological polymer adsorption tower 301 during regeneration to desorb H2S. The regenerated H2S enters the desorption tower 303 for buffering, and then passes through the condenser-liquid separator 304 to achieve gas-liquid separation. The final high-purity H2S is sent to the non-thermal plasma catalytic unit 5. The two adsorption towers operate alternately, one in use and one on standby, equipped with a programmable pneumatic shut-off valve to achieve continuous adsorption and desorption enrichment of H2S. The H2S removal rate is ≥99.9%, and the purity of enriched H2S is ≥95%.

[0075] As one implementation, the CO2 dual-tower capture unit 4 includes two coal-based activated carbon adsorption towers 401 arranged in parallel, a Roots-rotary vane vacuum regeneration unit 402, and a condensation and purification device 403. Each of the two coal-based activated carbon adsorption towers 401 is equipped with a desulfurization gas inlet, a purified tail gas outlet, and a CO2 outlet. The two coal-based activated carbon adsorption towers 401 adsorb alternately. After adsorption is completed, regeneration is performed. During adsorption, the desulfurization gas inlet and purified tail gas outlet of the corresponding coal-based activated carbon adsorption tower 401 are opened, and the CO2 outlet is closed. The desulfurization gas inlet and the desulfurization gas outlet are connected, and the purified tail gas is discharged from the purified tail gas outlet. During regeneration, the desulfurization gas inlet and the purified tail gas outlet of the corresponding coal-based activated carbon adsorption tower 401 are closed, and the CO2 outlet is opened. The CO2 outlet is connected in sequence to the Roots-rotary vane vacuum regeneration unit 402, the condensation and purification device 403, and the non-thermal plasma catalytic unit 5. The Roots-rotary vane vacuum regeneration unit 402 draws CO2 into the condensation and purification unit 403 through vacuuming, ultimately obtaining high-purity CO2 gas which is then sent to the non-thermal plasma catalytic unit 5. The two adsorption towers operate alternately, one in use and one on standby, equipped with a programmable pneumatic shut-off valve, achieving continuous adsorption and regeneration enrichment of CO2. The CO2 capture efficiency is ≥92%, and the purity of the enriched CO2 is ≥96%.

[0076] In one implementation, the non-thermal plasma catalytic unit 5 includes a static mixer 501, a preheater 502, a coaxial dielectric barrier discharge plasma catalytic reactor 503, a sulfur condenser / separator 504, and a sulfur flake generator 504 connected in sequence. The coaxial dielectric barrier discharge plasma catalytic reactor 503 is filled with a supported catalyst that can catalyze the directional conversion of H2S and CO2 into sulfur, CO, and H2. The H2S and CO2 regenerated by the H2S enrichment unit 3 and the CO2 dual-tower capture unit 4 enter the static mixer 501 for mixing, then enter the preheater 502 for heating, and then enter the coaxial dielectric barrier discharge plasma catalytic reactor 503 to complete the catalytic reaction, generating sulfur and syngas (CO and H2). The mixed gas then enters the sulfur condenser / separator 504, where sulfur vapor or sulfur mist is condensed and flows into the sulfur flake generator 505, cooling the liquid or molten sulfur into flakes, blocks, or granules. The remaining gas is the catalytic syngas.

[0077] As one implementation method, such as Figure 3 As shown, the coaxial dielectric barrier discharge plasma catalytic reactor 503 has a horizontal structure, including a stainless steel inner high-voltage electrode A01, a first high-purity quartz dielectric tube A02, a catalyst packed bed A03, a second high-purity quartz dielectric tube A04, a stainless steel external grounding electrode A05, an aluminum silicate insulation layer A06, a porous gas distributor A07, and a flange sealing end cap A08. The stainless steel inner high-voltage electrode A01, the first high-purity quartz dielectric tube A02, and the catalyst packed bed A03... The second high-purity quartz dielectric tube A04, the stainless steel external grounding electrode A05, and the aluminum silicate insulation layer A06 are concentrically arranged from the inside out to form a tubular structure. A porous gas distributor A07 is installed at both ends of the tubular structure, which is then sealed by flange end caps A08. The flange end caps at both ends are respectively provided with an inlet and an outlet. The inlet, the porous gas distributor A07 at the inlet end, the catalyst packed bed A03, the porous gas distributor A07 at the outlet end, and the outlet are sequentially connected. A supported catalyst is packed inside the coaxial dielectric barrier discharge plasma catalytic reactor 503. The reaction is carried out at atmospheric pressure, 120–180℃, and a reaction space velocity of 600–1000 h⁻¹. -1 Under the conditions of discharge voltage of 10-20kV, discharge frequency of 5-20kHz, and power density of 200-400W / L, a directional conversion reaction occurs. The reaction products are separated by two-stage condensation to obtain industrial sulfur with a purity of ≥99.5%. The gaseous product is catalytic synthesis gas with CO and H2 as the main components, wherein the H2S conversion rate is ≥99%, the CO2 conversion rate is ≥35%, and the sulfur selectivity is ≥95%.

[0078] Preferably, the sulfur condenser 504 is a two-stage sulfur condenser 504.

[0079] Furthermore, the H2S and CO2 mixed waste gas co-processing and resource recovery system also includes a gas turbine power generation unit 6 and a waste heat recovery unit 7. The gas turbine power generation unit 6 is used to generate electricity from catalytic synthesis gas and / or activated carbon purified tail gas. The waste heat recovery unit 7 is used to recover the high-temperature flue gas generated by the gas turbine and convert it into steam. The steam is then reused in the H2S and CO2 mixed waste gas co-processing and resource recovery system, or in activated carbon production plants, etc.

[0080] Furthermore, the H2S and CO2 mixed gas synergistic resource utilization treatment system also includes a DCS intelligent control unit, comprising an H2S leakage interlock module, an over-temperature and over-pressure interlock module, a combustible gas leakage interlock module, a tar exceeding standard interlock module, an adsorption tower switching interlock module, a gas turbine fault interlock module, and an emergency shutdown interlock module. The H2S leakage interlock module is used to monitor the H2S concentration in equipment and pipelines in real time and promptly detect equipment and locations where H2S leaks occur. The over-temperature and over-pressure interlock module is used to monitor the operating temperature and pressure of equipment in real time and promptly detect equipment operating at over-temperature or over-pressure conditions. The combustible gas leakage interlock module is used to monitor the content of combustible gases such as CH4, CO, and H2 in equipment and pipelines in real time and promptly detect equipment and locations where combustible gases leak. The tar exceeding standard interlock module is located at the outlet of the high-voltage electrostatic precipitator 203 and is used to monitor the tar content in real time and promptly detect situations where the tar content exceeds the standard at the outlet. The adsorption tower switching interlock module is used for two... The switching between the topological polymer adsorption tower 301 and the two coal-based activated carbon adsorption towers 401 is specifically as follows: Programmable pneumatic shut-off valves are installed at the pretreatment gas inlet, desulfurization gas outlet, steam inlet, and H2S outlet of the topological polymer adsorption tower 301, and at the desulfurization gas inlet, purified tail gas outlet, and CO2 outlet of the coal-based activated carbon adsorption tower 401. Based on the control of these programmable pneumatic shut-off valves, the switching between adsorption and regeneration processes is achieved, with a switching time ≤10s and no pressure fluctuations. The gas turbine fault interlock module is used to promptly detect gas turbine faults. The H2S leakage interlock module, over-temperature and over-pressure interlock module, combustible gas leakage interlock module, tar exceeding standard interlock module, and gas turbine fault interlock module are all connected to the emergency shutdown interlock module, enabling emergency shutdown control based on the detection status.

[0081] The DCS intelligent control unit is electrically connected to all transmitters, valves, pumps, heaters, plasma power supplies, and generator sets within the system, enabling fully automated control, real-time data acquisition, safety interlock protection, and remote monitoring.

[0082] The plasma power supply of the non-thermal plasma catalytic reactor is interlocked with the DCS system, and can automatically adjust the discharge voltage and frequency according to the feed gas flow rate and composition. The adjustment range is: voltage 10-20kV, frequency 5-20kHz.

[0083] All equipment and pipelines in the system that come into contact with sulfuric acid-containing gases are made of 316L stainless steel, and all electrical equipment is ExdⅡCT4 explosion-proof type, suitable for explosion-proof conditions in oil fields and factories.

[0084] This invention links the entire process with the activated carbon activation furnace control system, sets up nine safety interlocks, and has an interlock response time of ≤1s. It can achieve unattended continuous operation of the entire process, with an annual operating time of ≥7200h, and completely solves the problems of high safety risks and unstable operation of existing equipment.

[0085] For clarity, the present invention will be further described in detail below with reference to specific engineering embodiments and comparative examples. The following embodiments are only used to explain the present invention and are not intended to limit the scope of protection of the present invention.

[0086] This invention employs the following general performance evaluation methods: Gas component detection: Online detection using an Agilent 7890A gas chromatograph equipped with a flame photometric detector (FPD) and a thermal conductivity detector (TCD); Sulfur purity detection: Detection using the GB / T2449-2021 "Industrial Sulfur" standard; Tar content detection: Detection using the gravimetric method; Catalyst activity evaluation: Core indicators include H2S conversion rate, CO2 conversion rate, and sulfur selectivity; Pollutant emission detection: Detection using the GB 16297-1996 "Integrated Emission Standard for Air Pollutants"; Economic evaluation: Core indicators include investment cost, operating cost, annual revenue, and investment payback period.

[0087] Example 1: 5000 Nm 3 / h Coal-based activated carbon plant tail gas treatment project

[0088] Raw material gas source: tail gas from the potassium carbonate circulating activation production line of an activated carbon plant in Shanxi Province, with a processing capacity of 5000 Nm³. 3 / h, the feed gas composition is: CO 25 vol%, H2 18 vol%, CO2 11 vol%, H2S 0.35 vol%, tar 1200 mg / Nm³ 3 The exhaust gas temperature is 120℃, with N2 as the balance. The catalyst is a Ni3S2-MgS / AC composite catalyst, with a NiO loading of 10wt% and an MgO loading of 10wt% for the metal precursor. The catalyst is obtained through in-situ sulfidation activation of the metal precursor.

[0089] The specific process steps are as follows:

[0090] S1 Pretreatment: The tail gas from the potassium carbonate circulating activation production line of the activated carbon plant undergoes indirect cooling (cooling to below 60℃), cyclone dust removal, 35kV high-voltage electrostatic precipitator for tar, 1μm precision filtration, and dehydration treatment to obtain pretreated gas. The gas temperature is ≤40℃ and the dust concentration is ≤1mg / Nm³. 3 Water dew point -12℃, tar content 8mg / Nm³ 3 Tar removal rate ≥99%;

[0091] S2 H2S enrichment: H2S adsorption and desorption are completed in a dual-tower adsorption system of topological polymer adsorbent, using an alternating operation mode of one tower in use and one in standby. H2S is selectively adsorbed at 25℃ and normal pressure. After adsorption saturation, H2S is desorbed by hydrolysis with saturated steam at 115℃ and 0.2MPa. The desorbed gas is condensed and dehydrated to obtain high-concentration H2S gas with a purity of 95.2%. The total H2S removal rate is 99.92%, and the adsorbent regeneration efficiency is ≥98% after 100 cycles.

[0092] S3 CO2 Enrichment: CO2 adsorption and desorption are completed in a coal-based activated carbon dual-tower temperature-switching adsorption system, using an alternating operation mode of one tower in use and one in standby. CO2 is selectively adsorbed at 40℃ and normal pressure. After adsorption saturation, vacuum heating at 120℃ and a vacuum degree ≤100Pa is used for regeneration. The regenerated gas is then condensed and purified to obtain high-concentration CO2 gas with a purity of 96.4%, achieving a CO2 capture efficiency of 92.3%. The residual CO2 in the purified gas is ≤0.5 vol%.

[0093] S4 Catalytic Conversion: The high-concentration H2S and CO2 mixture obtained from step S3 is precisely mixed in a molar ratio of 2:1, preheated to 120°C, and then enters a coaxial dielectric barrier discharge nonthermal plasma catalytic reactor. The reactor is filled with a supported catalyst (Ni3S2-MgS / AC composite catalyst) capable of catalyzing the directional conversion of H2S and CO2 into sulfur, CO, and H2. The reaction is carried out at atmospheric pressure, 150°C, and a reaction space velocity of 800 h⁻¹. -1 Under conditions of discharge voltage of 15kV, discharge frequency of 10kHz, and power density of 200-400W / L, a directional conversion reaction occurs. The reaction products are separated by two-stage condensation to obtain industrial sulfur with a purity of 99.5%. The gaseous product is catalytic synthesis gas with CO and H2 as the main components, in which the H2S conversion rate is 99.2%, the CO2 conversion rate is 36.8%, and the sulfur selectivity is ≥95%.

[0094] S5 Power Generation: The catalytic synthesis gas and the activated carbon plant pretreatment gas produced after the pretreatment in step S1 are combined at a volume ratio of 1:3.33. After pressure stabilization, desulfurization, deoxygenation, and filtration, a total sulfur content of 12 mg / Nm³ is obtained. 3The high-quality syngas, with an oxygen content of 0.35 vol% and a pressure fluctuation of ≤±2%, is pressurized to 0.5 MPa and fed into a low-NOx gas turbine generator set for power generation. The generated electricity is used in the H2S and CO2 mixed waste gas co-processing system, oilfield gathering and transportation system, or the entire activated carbon production process. The low-NOx gas turbine has a rated power of 1.2 MW and a power generation capacity of 1.15~1.25 MW; the exhaust gas temperature is 350~450℃.

[0095] S6 Power Generation and Waste Heat Recovery: The heat from the high-temperature flue gas discharged from the gas turbine is recovered and fed into a shell-and-tube waste heat boiler to produce saturated steam. The waste heat boiler produces 2.5 t / h of 0.6 MPa saturated steam, of which 70% is used for the regeneration of H2S / CO2 adsorbent and 30% is used for supplemental heating of the activation furnace.

[0096] Execution result:

[0097] Environmental protection indicators: Total sulfur in the purified exhaust gas (exhaust gas after heat exchange in the S6 waste heat boiler is the final exhaust gas from the system) ≤ 5 mg / Nm³ 3 Particulate matter ≤10mg / Nm 3 With zero fugitive emissions, it fully meets the Class I standard of the "Integrated Emission Standard of Air Pollutants" GB16297-1996; resource utilization indicators: annual sulfur production of 1,600 tons, annual power generation of 9.6 million kWh, sulfur resource utilization rate of 100%, carbon resource utilization rate of 92.3%; energy consumption indicators: system self-heating rate of 100%, production electricity self-sufficiency rate of 100%, no external purchase of steam or electricity consumption; economic indicators: annual total revenue of 7.2 million yuan, investment payback period of 2.8 years; stability indicators: the system has been running continuously and stably for 720 hours without downtime or failure, and all indicators show no significant decline.

[0098] Example 2: 10000Nm 3 / h Shengli Oilfield Associated Gas Treatment Project

[0099] Raw material gas source: Associated gas from a block in Shengli Oilfield, with a processing capacity of 10,000 Nm³. 3 / h, the feed gas composition is: CH4 75.2 vol%, C2~C5 12.4 vol%, H2S 0.35 vol%, CO2 11.5 vol%, N2 0.55 vol%. Catalyst: same as in Example 1.

[0100] The specific process steps are as follows:

[0101] S1 Pretreatment: Associated gas from the oilfield undergoes sequential processing including cyclone dust removal, 1μm precision filtration, dehydration, and heavy hydrocarbon removal to obtain pretreated associated gas with a dust concentration ≤1mg / Nm³. 3Water dew point ≤ -10℃, heavy hydrocarbon content ≤ 0.5 vol.

[0102] S2-S4 are the same as in Example 1.

[0103] S5 power generation: The catalytic synthesis gas is sequentially subjected to pressure stabilization, desulfurization, deoxygenation, and filtration to obtain a total sulfur content of 12 mg / Nm³. 3 High-quality syngas with an oxygen content of 0.35 vol% and a pressure fluctuation of ≤±2%.

[0104] S6 is the same as in Example 1.

[0105] Operational results: Total sulfur in the purified exhaust gas was 12 mg / Nm³. 3 The CO2 residue is 0.42%, fully meeting the Class II gas standard of GB17820-2018 "Natural Gas"; the H2S removal rate is 99.91%, the CO2 capture and utilization rate is 92.1%, the annual sulfur production is 3,200 tons, and the annual power generation is 19.2 million kWh; the power generation fully covers the electricity consumption of the oilfield gathering and transportation system, the annual carbon emission reduction is 22,000 tons, and the investment payback period is 3.1 years.

[0106] Example 3: Verification Example of Wide Operating Condition Fluctuation

[0107] Raw material gas source: Same as in Example 1, with exhaust gas flow rate fluctuation of ±30% (3500~6500Nm). 3 / h), H2S concentration fluctuates 0.1–0.5 vol%, CO2 concentration fluctuates 8–15 vol%, tar content fluctuates 500–2000 mg / Nm³. 3 The process steps are the same as in Example 1.

[0108] Operating results: The system operated continuously and stably for 300 hours without any downtime or failure. The H2S removal rate was consistently ≥99.5%, the CO2 capture rate was ≥90%, the syngas concentration was ≥85%, and the generator load remained stable between 0.8 and 1.6 MW without any shutdown or tripping failures, verifying the wide operating condition adaptability of the process.

[0109] Example 4: Zn-Mo / AC catalyst adaptation example

[0110] Raw material gas source and process steps: Same as in Example 1, except that the catalyst is replaced with a ZnS-MoS2 / AC composite catalyst, and the catalyst corresponds to a ZnO loading of 8wt% and a MoO3 loading of 12wt%.

[0111] Operating results: H2S conversion rate 96.8%, CO2 conversion rate 24.5%, sulfur selectivity 96.2%, H2S removal rate 99.9%, CO2 capture rate 92%, proving that this process is compatible with all supported catalysts that can achieve H2S-CO2 conversion, and has extremely strong universality.

[0112] Comparative Example 1: Traditional Alkylamine Desulfurization and Decarbonization Process

[0113] Raw material gas source and processing capacity: Same as in Example 1, using methyl diethanolamine (MDEA) for desulfurization and decarbonization, the purified tail gas is directly discharged, and the tail gas is treated by combustion.

[0114] Operating results: H2S removal rate was 98.5%, CO2 removal rate was 90%, but sulfur and carbon resources could not be recovered, and there was no product revenue; 1,200 tons of desulfurization waste liquid were generated annually, and the hazardous waste disposal cost was RMB 1.8 million per year; 12,000 tons of steam were consumed annually, and 9.6 million kWh of electricity was purchased externally, with annual operating costs RMB 3.2 million higher than in Example 1; CO2 was directly released into the air, with no carbon emission reduction benefits, which does not meet the requirements of the dual-carbon policy.

[0115] Comparative Example 2: Existing one-step H2S-CO2 catalytic conversion process

[0116] Raw material gas source and processing capacity: Same as in Example 1, using Zn-Mo / Al2O3 catalyst from Shanxi Coal Chemical Institute, one-step mixing of tail gas feed, without stepwise enrichment process.

[0117] Operating results: H2S conversion rate was 82.3%, CO2 conversion rate was 18.6%, which was much lower than that of Example 1; the catalyst was deactivated by tar poisoning, and the activity retention rate was only 65.2% after 100 hours of operation, which could not be operated for a long period of time; there was no syngas power generation and waste heat recovery system, and the energy consumption was 38% higher than that of Example 1, resulting in no economic benefits.

[0118] Comparative Example 3: Direct Combustion Power Generation Process Using Activated Carbon Tail Gas

[0119] Raw material gas source and processing capacity: Same as in Example 1, using electrostatic precipitator + combustion furnace + steam turbine power generation process, and alkaline desulfurization to treat combustion tail gas.

[0120] Operating results: H2S combustion produces SO2, alkaline desulfurization generates 1,500 tons of waste liquid annually, causing serious secondary pollution; CO2 is directly released into the atmosphere, resulting in 11,000 tons of carbon emissions annually, with no carbon reduction benefits; the power generation efficiency is only 22%, 18 percentage points lower than the gas turbine power generation efficiency of Example 1, with an annual power generation of only 4.8 million kWh, which cannot meet the power demand for production; the annual operating cost is 4.2 million yuan higher than that of Example 1, with no product revenue.

[0121] Comparative Example 4: Wet desulfurization + pressure swing adsorption decarbonization process

[0122] Raw material gas source and processing capacity: Same as in Example 1, using the "wet desulfurization + pressure swing adsorption decarbonization" process, and the purified gas is combusted and discharged into the air.

[0123] Operating results: H2S removal rate 98.5%, CO2 removal rate 90%, annual desulfurization waste liquid production 1200 tons, hazardous waste disposal cost 1.5 million yuan / year; CO2 is directly vented into the air, with no resource recovery benefits; annual steam consumption 12,000 tons, annual operating cost is 3.5 million yuan higher than Example 1; CO and H2 in the tail gas are directly burned, energy utilization efficiency is only 20%, which is 18 percentage points lower than the power generation efficiency of Example 1.

[0124] In summary, the stepwise enrichment process of this invention is the core of achieving high conversion efficiency. Compared with the one-step process, the conversion rate of H2S and CO2 is increased by more than 1 times. The dual closed-loop design of this invention achieves energy self-sufficiency and zero pollution, completely solving the pain points of high energy consumption and secondary pollution in existing processes. The process of this invention can be adapted to a variety of catalyst systems and a wide range of operating condition fluctuations, with extremely strong universality and high value for industrial promotion.

Claims

1. A method for the synergistic and comprehensive resource utilization treatment of mixed H2S and CO2 waste gas, characterized in that, Includes the following steps: S1 Raw Material Grading Pretreatment: Pretreatment is performed on the mixed H2S and CO2 waste gas, which is at least one of the following: associated gas from oil fields and tail gas from activated carbon plants. Impurities in the mixed gas are removed, while H2S and CO2 are retained. The associated gas from oil fields includes CH4 70–80 vol%, C2–C5 10–15 vol%, H2S 0.1–0.5 vol%, CO2 5–15 vol%, and N2 balance. The tail gas from activated carbon plants includes CO 15–30 vol%, H2 10–20 vol%, CO2 8–15 vol%, H2S 0.1–0.5 vol%, and tar 500–2000 mg / Nm³. 3 The nitrogen balance is maintained at a temperature of 80–150°C. Selective adsorption and high concentration enrichment of H2S: H2S in the pretreated gas is adsorbed by a topological polymer adsorbent. After adsorption, the gas is desorbed by steam hydrolysis. The desorbed gas is then condensed to remove water and high concentration of H2S gas is obtained. S3 CO2 Dual-Tower Adsorption Capture and Purification: Coal-based activated carbon is then used to adsorb CO2 in the pretreated gas. After adsorption, vacuum heating regeneration is performed to obtain high-concentration CO2 gas. After the pretreated gas passes through steps S2 and S3 to adsorb H2S and CO2 in sequence, the remaining gas is the purified tail gas. S4 Non-thermal plasma synergistic catalytic directional conversion: The high-concentration H2S and CO2 mixture obtained from the regeneration in steps S2 and S3 is transported to the reactor. The reactor is equipped with a catalyst, and under the action of the catalyst, H2S and CO2 react to generate syngas and sulfur.

2. The method for synergistic and comprehensive resource utilization of H2S and CO2 mixed waste gas according to claim 1, characterized in that, It also includes, S5 delivers catalytic synthesis gas, or a mixture of catalytic synthesis gas and at least one of purified tail gas and activated carbon pretreatment gas, to the gas turbine for power generation to supplement the plant's electricity consumption. S6 waste heat closed-loop recovery: recovers the heat from the high-temperature flue gas discharged from the gas turbine and sends it to the shell-and-tube waste heat boiler to produce saturated steam.

3. The method for synergistic and comprehensive resource utilization of H2S and CO2 mixed waste gas according to claim 1, characterized in that, The associated gas pretreatment process in oilfields is as follows: the associated gas undergoes sequential processing including cyclone dust removal, 1μm precision filtration, dehydration, and heavy hydrocarbon removal to obtain pretreated associated gas with a dust concentration ≤1mg / Nm³. 3 The water dew point is ≤-10℃, and the heavy hydrocarbon content is ≤0.5 vol%. The pretreatment process for activated carbon production tail gas is as follows: the activated carbon production tail gas successively undergoes indirect cooling, cyclone dust removal, high-voltage electrostatic precipitator for tar, 1μm precision filtration, and dehydration treatment to obtain pretreated gas for the activated carbon plant. The gas temperature is ≤40℃, and the dust concentration is ≤1 mg / Nm³. 3 Water dew point ≤ -10℃, tar content ≤ 10mg / Nm 3 Tar removal rate ≥99%.

4. The method for synergistic and comprehensive resource utilization of H2S and CO2 mixed waste gas according to claim 1, characterized in that, In step S2, the adsorption and desorption of H2S are completed in a dual-tower adsorption system using a topological polymer adsorbent. An alternating operation mode of one tower in use and one in standby is employed. H2S is selectively adsorbed at ambient temperature and pressure. After adsorption saturation, desorption is performed using saturated steam at 110–120℃ and 0.2 MPa. The desorbed gas is condensed and dehydrated to obtain high-concentration H2S gas with a purity ≥95%, and the total H2S removal rate ≥99.9%. The topological polymer adsorbent is an aluminosilicate-based hyperbranched topological polymer modified with diethylenetriamine, with a hyperbranching degree ≥80%. Its static adsorption capacity for H2S is ≥2.3 mmol / g, its adsorption selectivity for H2S / CH4 is ≥200:1, its adsorption selectivity for H2S / N2 is ≥180:1, and its resistance to tar poisoning is ≥1000 mg / Nm³. 3 In step S3, CO2 adsorption and desorption are completed in a coal-based activated carbon dual-tower temperature-variable adsorption system, employing an alternating operation mode of one tower in use and one in standby. CO2 is selectively adsorbed at 35–45℃ and normal pressure. After adsorption saturation, regeneration is achieved through vacuum heating at 110–130℃ and a vacuum degree ≤100Pa. The regenerated gas is then condensed and purified to obtain high-concentration CO2 gas with a purity ≥96%, a CO2 capture efficiency ≥92%, and a CO2 residue in the purified gas ≤0.5 vol%. The coal-based activated carbon adsorbent is prepared from Zhundong long-flame coal using a potassium carbonate cyclic activation method, with a specific surface area ≥1100 m² / g and a pore volume ≥0.5 cm³. 3 / g, mechanical strength ≥94%, dynamic adsorption capacity for CO2 ≥2.6mmol / g, adsorption selectivity for CO2 / CH4 ≥35:

1.

5. The method for synergistic and comprehensive resource utilization of H2S and CO2 mixed waste gas according to claim 1, characterized in that, The high-concentration H2S and CO2 mixture obtained from step S3 is precisely mixed in a molar ratio of 2:1, preheated to 120°C in a preheater, and then enters a coaxial dielectric barrier discharge nonthermal plasma catalytic reactor. The reactor is filled with a supported catalyst capable of catalyzing the directional conversion of H2S and CO2 into sulfur, CO, and H2. The reaction is carried out at atmospheric pressure, 120–180°C, and a reaction space velocity of 600–1000 h⁻¹. -1 Under conditions of discharge voltage of 10–20 kV, discharge frequency of 5–20 kHz, and power density of 200–400 W / L, a directional conversion reaction occurs. The reaction products are separated by two-stage condensation to obtain industrial sulfur with a purity ≥99.5%. The gaseous product is catalytic synthesis gas with CO and H2 as the main components. The supported catalyst is a coal-based activated carbon supported composite catalyst, using Zhundong coal-based porous activated carbon prepared by potassium carbonate cyclic activation method as the carrier, and MgS, CaS, Ni3S2, Ni3S2-MgS or ZnS-MoS2 as active precursors.

6. A synergistic resource recovery system for mixed H2S and CO2 waste gas, characterized in that, The system includes a feedstock pretreatment unit, an H2S enrichment unit, a CO2 dual-tower capture unit, a non-thermal plasma catalysis unit, a gas turbine power generation unit, and a waste heat recovery unit. The feedstock pretreatment unit is used to remove dust, water, condensate oil, and heavy hydrocarbons from associated gas from oilfields, ensuring that the dust concentration in the associated gas is ≤1 mg / Nm³. 3 Water dew point ≤ -10℃, heavy hydrocarbon content ≤ 0.5 vol%; or used to remove dust, water, and tar from the tail gas of coal-based activated carbon production, so that the tail gas temperature is ≤ 40℃ and the dust concentration is ≤ 1 mg / Nm³. 3 Water dew point ≤ -10℃, tar content ≤ 10mg / Nm 3 The raw material pretreatment unit is sequentially connected to the H2S enrichment unit and the CO2 dual-tower capture unit. The H2S enrichment unit is used to adsorb and regenerate H2S in the H2S and CO2 mixed waste gas, and the CO2 dual-tower capture unit is used to absorb and regenerate CO2 in the H2S and CO2 mixed gas. The regeneration gas outlets of the H2S enrichment unit and the CO2 dual-tower capture unit are both connected to the non-thermal plasma catalytic unit, which sends the regenerated H2S and CO2 into the non-thermal plasma catalytic unit. Under the action of the catalyst, the non-thermal plasma catalytic unit converts H2S and CO2 into sulfur, CO and H2 in a directional manner. The gas turbine power generation unit is used to generate electricity from the catalytic synthesis gas and / or activated carbon purified tail gas. The waste heat recovery unit is used to recover the high-temperature flue gas generated by the gas turbine and convert it into steam.

7. The synergistic resource recovery system for H2S and CO2 mixed waste gas as described in claim 1, characterized in that, The raw material pretreatment unit includes an associated gas pretreatment unit for oil fields and a tail gas pretreatment unit for coal-based activated carbon production. The associated gas pretreatment unit for oil fields includes a first gas-liquid separator, a first cyclone separator, a first 1μm coalescing precision filter, a first molecular sieve dehydration tower, a condenser, and a second gas-liquid separator connected in sequence. The tail gas pretreatment unit for coal-based activated carbon production includes a gas cooler, a second cyclone separator, a high-voltage electrostatic precipitator for tar, a second 1μm precision filter, and a second molecular sieve dehydration tower connected in sequence.

8. The synergistic resource recovery system for H2S and CO2 mixed waste gas as described in claim 1, characterized in that, The H2S enrichment unit includes two parallel topological polymer adsorption towers, a steam generator, a desorption tower, and a condenser-liquid separator. Each of the two topological polymer adsorption towers is equipped with a pretreated gas inlet, a desulfurization gas outlet, a steam inlet, and an H2S outlet. The two topological polymer adsorption towers adsorb alternately, and regeneration occurs after adsorption is complete. During adsorption, the pretreated gas inlet and desulfurization gas outlet of the corresponding topological polymer adsorption tower are open, while the steam inlet and H2S outlet are closed. The pretreated gas inlet is connected to the associated gas pretreatment unit of the oilfield or the tail gas pretreatment unit of coal-based activated carbon production, and the desulfurization gas outlet is connected to the CO2 dual-tower capture unit. During regeneration, the pretreated gas inlet and desulfurization gas outlet of the corresponding topological polymer adsorption tower are closed, while the steam inlet and H2S outlet are open. The steam inlet is connected to the steam generator, and the H2S outlet is sequentially connected to the desorption tower, the condenser-liquid separator, and the non-thermal plasma catalytic unit. The CO2... The dual-tower adsorption unit comprises two coal-based activated carbon adsorption towers connected in parallel, a Roots-rotary vane vacuum regeneration unit, and a condensation and purification device. Each of the two coal-based activated carbon adsorption towers is equipped with a desulfurization gas inlet, a purified tail gas outlet, and a CO2 outlet. The two towers adsorb adsorption gases alternately, and regeneration occurs after adsorption is complete. During adsorption, the desulfurization gas inlet and purified tail gas outlet of the corresponding coal-based activated carbon adsorption tower are open, while the CO2 outlet is closed. The desulfurization gas inlet and outlet are connected, and the purified tail gas exits through the purified tail gas outlet. During regeneration, the desulfurization gas inlet and the purification tail gas outlet of the corresponding coal-based activated carbon adsorption tower are closed, while the CO2 outlet is opened. The CO2 outlet is sequentially connected to the Roots-rotary vane vacuum regeneration unit, the condensation purification device, and the non-thermal plasma catalytic unit. The non-thermal plasma catalytic unit includes a static mixer, a preheater, a coaxial dielectric barrier discharge plasma catalytic reactor, a sulfur condenser separator, and a sulfur flake machine, which are sequentially connected. The coaxial dielectric barrier discharge plasma catalytic reactor is filled with a supported catalyst that can catalyze the directional conversion of H2S and CO2 into sulfur, CO, and H2.

9. The synergistic resource recovery system for H2S and CO2 mixed waste gas as described in claim 1, characterized in that, The coaxial dielectric barrier discharge plasma catalytic reactor is a horizontal structure, comprising a stainless steel inner high-voltage electrode, a first high-purity quartz dielectric tube, a catalyst-packed bed, a second high-purity quartz dielectric tube, a stainless steel external grounding electrode, an aluminum silicate insulation layer, a porous gas distributor, and a flange sealing end cap. The stainless steel inner high-voltage electrode, the first high-purity quartz dielectric tube, the catalyst-packed bed, the second high-purity quartz dielectric tube, the stainless steel external grounding electrode, and the aluminum silicate insulation layer are arranged concentrically from the inside to the outside to form a tubular structure. A porous gas distributor is installed at both ends of the tubular structure and then sealed by a flange sealing end cap. An inlet and an outlet are respectively provided on the flange sealing end caps at both ends. The inlet, the porous gas distributor at the inlet end, the catalyst-packed bed, the porous gas distributor at the outlet end, and the outlet are connected in sequence.

10. The synergistic resource recovery system for H2S and CO2 mixed waste gas as described in claim 1, characterized in that, The H2S and CO2 mixed gas synergistic resource utilization treatment system also includes a DCS intelligent control unit, comprising an H2S leakage interlock module, an over-temperature and over-pressure interlock module, a combustible gas leakage interlock module, a tar exceeding standard interlock module, an adsorption tower switching interlock module, a gas turbine fault interlock module, and an emergency shutdown interlock module; H2S The leakage interlock module is used to monitor the H2S concentration in equipment and pipelines in real time and promptly detect H2S leaks and their locations. The over-temperature and over-pressure interlock module is used to monitor the operating temperature and pressure of equipment in real time and promptly detect equipment operating at over-temperature or over-pressure. The combustible gas leakage interlock module is used to monitor the combustible gas content in equipment and pipelines in real time and promptly detect combustible gas leaks and their locations. The tar exceeding standard interlock module is installed at the outlet of the high-voltage electrostatic precipitator to monitor the tar content in real time and promptly detect tar exceeding the standard at the outlet. The adsorption tower switching interlock module is used to switch between two topological polymer adsorption towers and two coal-based activated carbon adsorption towers. Based on the control of the corresponding programmable pneumatic shut-off valves, it realizes the switching of adsorption and regeneration processes, with a switching time ≤10s and no pressure fluctuations. The gas turbine fault interlock module is used to promptly detect gas turbine faults. The H2S leakage interlock module, over-temperature and over-pressure interlock module, combustible gas leakage interlock module, tar exceeding standard interlock module, and gas turbine fault interlock module are all connected to the emergency shutdown interlock module to perform emergency shutdown control based on the detection status.

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